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OUTLINES 


BASED  IN  PART  UPON  RICHES'  MANUEL  de  CHIMIE, 


C.  GILBERT  WHEELER, 
\« 

Professor  of  Chemistry  in  the  University  of  Chicago. 


A,  S,  BARNES  &  00,, 
NEW  YORK  AND  CHICAGO. 

'877. 


OTHER  WORKS  BY  PROF.  WHEELER. 


DETERMINATIVE  MINERALOGY.    A  practical  guide  to  the  recogni- 
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IN   PREPARATION. 

THE  CHEMISTRY  OF  BUILDING  MATERIALS. 


COPYRIGHT 
C.;  G  iLB,E,tlt  ;.W  HEELER. 

;:>;>';,'.•<  1877.  • 


PREFACE. 


Organic  chemistry  has  not  as  yet  secured  in  Ameri- 
can colleges  sufficiently  pronounced  attention  to  create 
a  demand  for  text-books  of  considerable  size  or  ex- 
tended scope.  In  these  simple  Outlines,  therefore,  no 
more  has  been  attempted  than  this  circumstance  would 
appear  to  warrant.  It  is  hoped  that  the  necessary 
conciseness  in  method  and  form  of  expression  has  not 
resulted  in  any  important  sacrifice  of  perspicuity  in 
thought  or  arrangement. 

It  would  have  been  easier  to  prepare  a  larger  work. 
From  the  bewildering  wealth  of  results  afforded  by  the 
labors  of  investigators  in  this  branch  of  science,  the  ap- 
propriate selection  of  that  suited  to  the  wants  of  stu- 
dents was  by  no  means  an  easy  task. 

It  is  assumed  in  these  Outlines  that  those  entering 
upon  the  study  of  Organic  Chemistry  have  previously 
made  themselves  acquainted  with  Inorganic  Chemistry 
as  taught  by  some  modern  author,  such  as  Miller  or 
Barker,  or  have  at  least  become  familiar  with  the  gen- 
eral principles  of  modern  chemical  philosophy.  The 
author  taking  this  for  granted,  has  not,  therefore,  en- 
cumbered the  work  with  a  restatement  of  that  which 
appertains  to  the  theory  of  chemistry  in  general. 

In  addition  to  the  organic  portion  of  Riche's  Man- 
uel de  Chimie,  a  translation  of  which  by  the  author 

237364 


PREFACE. 

has  served  in  part  as  basis  for  these  Outlines,  the 
works  of  Miller,  Fownes,  •  Williamson,  Roscoe,  and 
others  have  been  freely  used,  while  the  chemical 
journals  of  Europe  and  America,  including  their  latest 
numbers,  have  been  consulted  and  the  data  which 
they  afforded  utilized. 

For  the  benefit  of  any  who  may  care  to  read  the  full 
original  papers  from  which  are  taken  the  abridged  ex- 
cerpta  of  recent  articles  there  are  given  references, 
within  parentheses,  to  a  list  of  authorities  to  be  found 
in  the  author- s  work  on  Medical  Chemistry. 

Lest  any  regard  the  number  of  characteristic  re- 
actions of  the  more  important  compounds  as  insuffi- 
cient, it  should  be  stated,  that  it  was  not  within 
the  plan  of  the  author  to  adapt  this  work  to  the 
requirements  of  an  analytical  manual.  Not  more 
than  two  or  three  analytical  tests  are  therefore  given 
as  a  rule,  and  even  this  number  only  in  the  case  of  the 
leading  compounds.  A  similar  explanation  might  be 
proffered  to  any  who  may  miss  the  full  technical  de- 
tails relative  to  certain  compounds  which  are  usually 
given  in  works  on  applied,  or  technological  chemistry. 

Throughout  the  work,  the  centigrade  thermometer 
and  the  metric  system  of  weights  and  measures  are 
employed,  unless  otherwise  specifically  stated. 

C.  GILBERT  WHEELER. 

UNIVERSITY  OF  CHICAGO,  October,  1877. 


CONTENTS. 


INTRODUCTORY,       -  7 

CLASSIFICATION  OF  ORGANIC  COMPOUNDS,  10 

HOMOLOGOUS  SERIES,  -                                               12 

HYDROCARBONS,      -  18 

ALCOHOLS,       -  44 

MONATOMIC,  46 

DIATOMIC,  58 

TRIATOMIC,  64 

ETHERS,  69 

ALDEHYDS,  85 

ACIDS,  90 

MONATOMIC,  96 

POLYATOMIC,  -                                             112 

ALKALOIDS  OR  BASES,  -      127 

ARTIFICIAL,  132,  170 

"        NATURAL,  -      137 

NEUTRAL  FATTY  BODIES,  174 

SUGARS,  -      181 

GLUCOSIDES,  193 

VEGETABLE  CHEMISTRY,  199 

CELLULOSE,  -  205 

STARCH,  -      210 

DEXTRIN,  214 

GUMS,      -  -      216 


ORGANIC  CHEMISTRY. 


rNTEODUCTOEY. 

Organic  chemistry  is  the  science  of  the  compounds 
of  carbon. 

Only  a  small  number  of  other  elements  are  met 
with  in  natural  organic  substances;  they  are  hydrogen, 
oxygen  and  nitrogen,  sometimes  also,  sulphur,  phos- 
phorus, and  very  rarely  certain  other  elements. 

Chemists  have  succeeded  in  incorporating  most  of 
the  elemental  substances  in  organic  bodies,  yet  the 
larger  number  even  of  the  artificial  compounds  include 
only  the  four  elements  first  named. 

Paraffine  is  found  by  analysis  to  contain  only  carbon 
and  hydrogen,  and  is  therefore  called  a  hydrogen- 
carbide.  The  hydrocarbides  are  compounds  so  stable 
and  fundamental  that  some  chemists,  as  Schorlemmer 
for  instance,  have  even  defined  organic  chemistry  as 
"the  chemistry  of  hydrocarbons  and  their  derivatives." 

From  alcohol,  or  sugar,  we  may  obtain  carbon  and 
water.  These  bodies  therefore  are  composed  of  three 
elements:  carbon,  hydrogen  and  oxygen,  and  are  called 
carbohydrates  ;  though  by  some  chemists,  this 
term  is  restricted  to  those  compounds  containing  car- 


8  ORGANIC     CHEMISTRY. 

bon  with  hydrogen,  and  oxygen  in  such  proportions  as 
would  form  water. 

If  albumen  is  decomposed  by  heat,  the  result  is  not 
only  carbon  and  water,  but  also  ammonia ;  this  sub- 
stance accordingly  is  nitrogenous. 

The  number  of  organic  bodies  is  very  great.  As  they 
are  composed  of  a  small  number  of  elements  only,  it 
may  be  concluded  that  the  latter  unite  in  a  very  great 
variety  of  proportions  ;  it  is  therefore  of  much  impor- 
tance to  know  the  molecular  grouping  of  these  ele- 
ments. The  mere  fact  that  the  kind  and  number  of 
elements  entering  into  a  compound  are  known,  is  not 
sufficient  proof  that  its  molecular  structure  is  really 
determined.  Synthesis  must  often  be  employed  to 
confirm  the  results  of  analysis. 

Berthelot  has  specially  occupied  himself  with  the 
synthesis  of  organic  bodies,  and  has  artificially  produced 
a  great  number  of  them.  Other  chemists  have 
experimented  in  the  same  direction  during  the  last  15 
or  20  years.  However,  Gerhard t's  opinion  advanced 
in  1854;  viz.,  "  The  vital  force  alone  operates  by  syn- 
thesis and  reconstructs  the  edifice  demolished  by 
chemical  affinity,"  has  ceased  to  be  held  as  true. 

ISOMEEISM. 

Carbon,  hydrogen,  oxygen  and  nitrogen  are  not  only 
capable  of  uniting  in  a  great  variety  of  proportions, 
but  these  elements  also  furnish  numerous  isomeric 
bodies  ;  these  comprise  substances  which,  while  com- 


ISOMERISM.  9 

posed  of  the  same  elements,  have  different  properties. 
Sometimes  the  physical  properties  alone  are  different ; 
we  then  have  physical  isomerism. 

When  the  chemical  properties  themselves  are  modi- 
fied, this  is  denominated  chemical  isomerism.  Of  the 
latter,  two  kinds  are  recognized. 

I.  Polymerism;  cyanogen   and  paracyanogen  are 
examples  of  this  variety  of  isomerism ;  the  latter  is  to 
be    considered    as    cyanogen,    CN  condensed,    thus 
(CN)n ;  it  is  a  poly  meride  of  cyanogen.     The  weight  of 
the  molecule  of  these  two  substances  is  therefore  dif- 
ferent. 

II.  Metamerism.     At  other  times  the  isomerism 
results  from  a  different  grouping  of  elements  in  the 
compound,  the  molecular  weight  remaining  the  same. 

We  will  illustrate  this  by  two  examples  : 

a)  Methyl  acetate, 
and  b)  Ethyl  formiate. 

Acetic  acid  =  H-0-C3H30. 

Methyl  hydrate,  or  methyl  alcohol=H-O-CH3. 

When  these  two  bodies  react  they  furnish  water  and 
methyl  acetate,  CH3-O-C2H3O=<53H602. 

Formic  acid=H-O-CHO. 

Ethyl  hydrate,  or  ethyl  alcohol=H-O-C2H5. 

JNTow  formic  acid  contains  CH3  less  than  acetic  acid, 
and  hydrate  of  ethyl  contains  one  molecule  of  CH2 
more  than  does  hydrate  of  methyl.  As  these  substan- 
ces in  reacting  lose  one  molecule  of  water,  it  is  there- 
fore clear  that  the  compound  obtained  will  have,  like 
the  preceding  one,  the  formula  C3H6Oj>.  But  these 


10  ORGANIC    CHEMISTRY. 

two  products  are  not  identical  substances,  for  the  for- 
mer treated  with  alkalies  regains  the  molecule  of  water 
which  it  had  lost,  reforming  acetic  acid  and  methyl  hy- 
drate, while  the  latter  regenerates  formic  acid  and  ethyl 
hydrate. 

These  bodies  accordingly  differ  in  the  arrangement 
of  their  molecule ;  they  are  called  metameric  bodies* 

Finally  there  exist  bodies  which  are  isomeric,  prop- 
erly so-called,  possessing  the  same  formula,  having  the 
same  general  reactions,  the  same  chemical  functions, 
and  which  differ  only  in  a  very  few,  chiefly  physical, 
properties  :  such  are  oil  of  turpentine  and  oil  of  lemon, 
each  having  the  formula  C10H16. 

CLASSIFICATION    OF    ORGANIC    COM- 
POUNDS. 

CHEMICAL  TYPES. — The  idea  of  referring  organic  bod- 
ies to  some  simple  model,  or  type,  was  originally  work- 
ed out  by  Laurent  and  Gerhardt,  18^6-53,  though  the 
germs  of  their  ideas  011  classification  are  to  be  found  in 
the  earlier  papers  of  the  distinguished  American 
chemist  T.  Sterry  Hunt.  (Am.  Jour.  Sci.  [2]  xxxi.) 

The  four  principal  types  are  : 

TT/     \ 

I.  The  hydrogen  type,  TT,  >  or  H2. 

II.  The  oxide  or  water  type,  5,  1  O' '  orH2O. 

H/  ) 

III.  The  nitride  or  ammonia  type,H    V  N' ' '  orII3N. 


ORGANIC     TYPES.  11 

BM 

IV.    The  marsh  gas  type  ^  ',\  CIV  or  H4C. 

H'j 

Of  the  leading  groups  of  organic  bodies,  we  refer  to 
the  hydrogen  type:  hydrocarbides,  aldehyds  and  the 
compounds  of  metals  and  metalloids  with  organic 
radicals. 

To  the  water  type  are  referred  the  alcohols,  ethers, 
rnercaptans  and  anhydrides. 

To  the  ammonia  type  belong  the  amides,  amines, 
and  alkalamides,  all  of  which  are  denominated  com- 
pound ammonias. 

Marsh-gas  is  the  type  to  which  carbon  dioxide  is 
referred,  as  well  as  some  of  the  more  complex  organo- 
metallic  bodies. 

Farther  details  as  to  the  relation  of  each  of  these 
classes  of  compounds  to  their  respective  types  will  be 
given  as  each  particular  class  is  studied. 

Besides  the  simple  type,  Kekule  has  proposed  com- 
pound types  formed  by  the  combination  of  two  of  the 
four  types  already  given.  Thus  the  types  of  ammonia 
and  water  combined  serve  as  a  pattern  for  carbamic 
and  oxamic  acids: 

JJ  '   )  Carbamic  acid.  Oxamic  Acid. 


o 


12  ORGANIC     CHEMISTRY. 


HOMOLOGOUS   SERIES. 


The  members  of  a  series  of  compounds  which  have 
the  common  difference  of  CH2  are  said  to  be  homolo- 
gous. Two  or  more  such  homologous  series  are  termed 


The  first  idea  of  progressive  series  in  organic 
chemistry  was  enunciated  by  James  Schiel,  of  St. 
Louis,  Mo.,  in  1842.  It  was  afterwards  adopted  by 
Gerhardt  unchanged,  save  only  in  name.  (100-5-195.) 

The  subjoined  table  will  illustrate  the  nature  of  these 
series.  Each  vertical  column  forms  a  homologous 
series  in  which  the  terms  differ  by  CH2,  and  each  hori- 
zontal line  an  isologous  series  in  which  the  successive 
terms  differ  by  H2.  The  bodies  of  these  last  series  are 
designated  as  the  monocarbon,  dicarbon  group,  etc. 

C  H4    C  H2 

Cg-Llg        Cg-H.^        Cgllg 

C3H8    C3H6    C3H4    C3H2 
C4H10  C4H8    C4H6    C4H4  C4H2 
^5^-12  C5H10  C5H8    C5H6  C5H4  C5H2 
CeH14  C6H12  C6H10  C6H8  C6H6  C6H4  C6H2 

The  terms  of  the  same  homologous  series  resemble 
one  another  in  many  respects,  exhibiting  similar  trans- 
formations under  the  action  of  given  re-agents,  and  a 
regular  gradation  of  properties  from  the  lowest  to  the 
highest ;  thus,  of  the  hydro-carbons,  Cn  H2n+2,  the  low- 
est terms  CH4i  C2H6,  and  C3H8i  are  gaseous  at  ordinary 
temperatures,  the  highest  containing  20  or  more  car- 


HOMOLOGOUS     SERIES. 


13 


bon-atoms,  are  solid,  while  the  intermediate  com- 
pounds are  liquids,  becoming  more  and  more  viscid  and 
less  volatile,  as  they  contain  a  greater  number  of  car- 
bon-atoms, and  exhibiting  a  constant  rise  of  about  20° 
C.  (36°  F.)  in  their  boiling  points  for  each  addition  of 
CH2  to  the  molecule. 

The  individual  series  are  given  in  the  following  ta- 
ble, with  the  names  proposed  for  them  by  A.  W. 
Hoffmann: 


Methane    Methene 

O I  j_4  0  Jig 

Ethane       Ethene 


Propane 
C3H8 

Quartane 
C4H10 

Quintane 

C5H12 

Sextane 


Propene 

C3H6 
Quartene 

C4H8 
Quintene 

C5H10 
Sextene 

C6H12 


Ethine 

C2H2 
Propine 

03H4 
Quartine 

04H6 
Quintine 

C3H3 
Sextine 


Propone 


Quartone  Quartune 
04x14  ^Hjj 

Quintone  Quintune 
05H6 

Sextone 


CH 


05H4 

Sextune 
C6H6 


The  formulae  in  the  preceding  tables  represent  hydro- 
carbons all  of  which  are  capable  of  existing  in  the 
separate  state,  and  many  of  which  have  been  actually 
obtained.  They  are  all  derived  from  saturated  mole- 
cules, CnH2n4.2i  by  abstraction  of  one  or  more  pairs  of 
hydrogen-  atoms. 

But  a  saturated  hydrocarbon,  CH4i  for  example,  may 


14  ORGANIC    CHEMISTRY. 

give  up  1,  2,  3,  or  any  number  of  hydrogen-atoms  in 
exchange  for  other  elements  ;  thus  marsh  gas,  CH4, 
subjected  to  the  action  of  chlorine  under  various  cir- 
cumstances, yields  the  substitution-products, 

CH8C1,         CHCaCla,         CHC18,          CC14, 

which  may  be  regarded  as  compounds  of  chlorine  with 
the  radicles, 

(CH,)',      (CH,)",       (OH,)'",      0"; 

and  in  like  manner  each  hydrocarbon  of  the  series, 
CnIi2n+2,  maJ  yield  a  series  of  radicles  of  the  forms, 


each  of  which  has  an  equivalent  value,  or  combining 
power,  corresponding  with  the  number  of  hydrogen- 
atoms  abstracted  from  the  original  hydrocarbon.  Those 
of  even  equivalence  contain  even  numbers  of  hydro- 
gen-atoms, and  are  identical  in  composition  with  those 
in  the  table  above  given  ;  but  those  of  uneven  equiva- 
lence contain  odd  numbers  of  hydrogen-atoms,  and 
are  incapable  of  existing  in  the  separate  state,  except, 
perhaps,  as  double  molecules. 

These  hydrocarbon  radicles  of  uneven  equivalence 
are  designated  by  Hoffmann,  with  names  ending  in  yl, 
those  of  the  univalent  radicles  being  formed  from 
methane,  ethane,  &c.,  by  changing  the  termination 


HOMOLOGOUS     SERIES.  15 

ane  into  yl ;  those  of  the  trivalent  radicles  by  chang- 
ing the  final  e  in  the  names  of  the  bivalent  radicles, 
methene,  &c.,  into  ylf  and  similarly  for  the  rest.  The 
names  of  the  whole  series  will  therefore  be  as  follows  : 

CH4  (CH8)'  (CH2)"  (OH)'" 

Methane  Methyl  Methene  Methenyl 

C2H6  (C2H5)'  (C2H4)"  (C2H3)'" 

Ethane            Ethyl  Etliene  Ethenyl 

CSH8  (CaH,)'  (C3H6)"  (C3H5)'" 

Propane            Propyl  Propene  Propenyl 

&c.  &c.  &c. 


From  these  hydrocarbon  radicles,  others  of  the 
same  degree  of  equivalence  may  be  derived  by  partial 
or  total  replacement  of  the  hydrogen  by  other  elements, 
or  compound  radicles.  Thus  from  propyl,  C3H7,  may 
be  derived  the  following  univalent  radicles: — 

C3H6C1                    C8H8014  C3H50 

Chloropropyl       Tetrachloropropyl  Oxy  propyl 

C3H2C136               C3H6(CN)'  C3H6(N02) 

Trichloroxypropyl        Cyanopropyl.  Nitropropyl 

C8H4(NHa)0            C3H6(CH3)  C3H5(C2H5)2 

Amidoxy  propyl      Methylpropyl  Diethylpropyl. 

From  the  radicles  above  mentioned,  all  well-defined 
organic  compounds  may  be  supposed  to  be  formed  by 
combination  and  substitution,  each  radicle  entering 
into  combination,  just  like  an  elementary  body  of  the 
same  degree  of  equivalence. 


16  OEGANIO    CHEMISTRY. 

TABLE  TO  ILLUSTRATE  THE  ARRANGEMENT  OF  THE  MOKE 


Series. 

Hydro- 
carbons. 

Sulphides. 

Chlorides  or 
Haloid    Ethers. 

Alcohols. 

General 
Formula. 

CriH.2n 

CnH2«  +  i  I  tt 
CnH2»+i  fs 

CttH2W+iCl 

Cnttm+i£0 

i.    C    H2 

(C  H3)2S 

C  H3  Cl 

C  H3  HO 

2.    C2  H4 

(C2HS)2S 

C2HS  Cl 

C2Hs  HO 

3-    C3H6 

C3H7  Cl 

C3H7  HO 

4.    C4Hg 

C4H9  Cl 

C4Ho  HO 

5.    GS  Hio 

(C5Hii)2S 

CsHiiCl 

CsHiiHO 

6.     C6  Hi2 

C6Hi3HO 

7.    C7Hi4 

8.    Cg  Hi6 

CSHifCl 

CsHi7HO 

9.    Cg  HiS 

10.    CioH2o 

Types 

H| 

H  }  0 

HI 

II  |  0 

Hj 

Hf  u 

H  f 

\ 

OKGANIC    COMPOUNDS.  17 

IMPORTANT  ORGANIC  COMPOUNDS  IN  HOMOLOGOUS  SERIES. 


Mercaptans. 

Aldehyde. 

Acids. 

Simple  Ethers. 

Compound  Ethers. 

. 

H           \S 

CnH2n-i  O  I 
H              I 

C«H2»-iO  j  ~ 
Hf° 

CnH2/i+i  t 

CnH2w-  zO  f 

C  H3  HS 

C    H    0,H 

HO    H    02 

(C  H3)20 

C  H3  C    H    02      i. 

C2Hs  HS 

C2  H3  O,H 

HC2  H3  02 

(C2H5,20 

C2H5  C2  H3  02      2. 

C3  HS  0,H 

HC3  HS  0-i 

C2Hs  C3  HS  02      3. 

C4H9  HS 

•C4  H7  O,H 

HC4  H7  O2 

C2Hs  C4  H7  02      4. 

CsHnHS 

Cs  H9  O,H 

HCS  H9  O2 

(CsH9)20 

CsHuCs  H9  02      5. 

C6  HiiO,H 

HC6  HnO2 

C2HS  C6  HiiO2      6. 

C7H,30,H 

HC7  Hi3O2 

C2HS  C7  Hi3O2      7. 

HCg  HisO2 

C2HS  Cg  HisO2      8. 

HC9  Hi7O2 

C2Hs  C9  Hi7O2      9. 

11  !  o 
Hf° 

CioHi9H,0 

HCioHi9O2 

(CioHi9)2O 

C2HS  CioHi9O2     10. 

H  1 
Hf 

H     |     Q 

H(  0 
Hf° 

H     /      Q 

18  ORGANIC     CHEMISTRY. 

CAEEIDES     OF    HYDKOGEK 

The  origin  or  preparation  of  these  compounds,  also 
called  hydrocarbides,  and  their  properties,  physical 
and  chemical,  all  differ  largely. 

They  are  unlike  the  hydrogen  combinations  studied 
in  inorganic  chemistry  inasmuch  as  they  possess  but 
feeble  chemical  energy  Among  the  carbides  are: 
acetylene,  marsh-gas  or  methane,  ethylene,  oil  of  tur_ 
pentine  and  of  lemon,  benzol,  iiaphthalin,  petroleum, 
caoutchouc,  gutta-percha,  etc. 

The  hydrocarbides  will  be  divided  into  six  series, 
they  are  all  built  upon  the  type  of  a  molecule  of  hy- 
drogen, or  H'  ) 

ir  r 

FIKST  SEEIES. 

General  Formula,  CnH-2n_2. 
ACETYLENE,  OB   DIHYDROGEN    DICARBIDE. 

Discovered  by  Davy  and  composition  determined  by  Berthelct. 

Formula,  C2Ha- 

Specific  Gravity,  0.92.    Density,  13.    Molecular  weight,  26. 

Direct    combination  of  Carbon    and  Hydrogen. 

Up  to  comparatively  recent  times  it  has  been  con- 
sidered impossible  to  unite  carbon  and  hydrogen  di- 
rectly. Berthelot,  however,  succeeded  in  doing  this  in 
the  year  1863. 

PREPARATION. — The  apparatus   which  he  employed 


CARBIDES    OF    HYDKOGEJS.  19 

in  this  remarkable  synthesis,  consisted  of  a  glass  flask, 
provided  with  two  lateral  tubulures  through  which 
passed  two  metallic  rods,  terminating  in  carbon  points, 
and  which  approached  so  as  to  form,  when  connected 
with  a  powerful  battery,  an  electric  arc.  The  corks 
through  which  these  rods  passed  were  provided  with 
another  opening  each,  to  which,  a  tube  was  adapted. 
Through  one  of  these  tubes  hydrogen  was  admitted 
and  through  the  other  the  products  of  the  reaction 
passed  as  they  were  formed. 

The  gas  was  collected  in  a  solution  of  cuprous 
chloride  in  ammonia.  A  red-precipitate,  acetylide  of 
copper  was  formed,  which  was  thrown  upon  a  filter  and 
treated  with  hydrochloric  acid  in  a  flask,  whereupon 
acetylene  was  set  free. 

Many  organic  compounds  produce  acetylene  on 
subjecting  their  vapors  to  the  action  of  electric  dis- 
charges. 

Acetylene  is  also  produced,  as  a  rule,  whenever  or- 
ganic matter  is  decomposed  by  heat. 

PROPERTIES. — Acetylene  is  a  colorless  gas,  having  a 
disagreeable  odor.  It  is  moderately  soluble  in  water, 
and  has  not  been  liquified.  It  is  decomposed,  at  about 
the  temperature  at  which  glass  melts,  into  carbon, 
hydrogen,  ethylene,  ethyl  hydride  and  condensed 
hydrocarbides,  among  which  Berthelot  has  found  ben- 
zol. Thenard  has  recently  obtained  it  both  as  a  liquid 
and  a  vitreous  solid.  (9 — 78 — 219.) 

Acetylene  burns  with  a  fuliginous  flame.  It  de- 
tonates violently  and  witho.it  residue  when  mixed  with 


20  ORGANIC     CHEMISTRY, 

2.5  volumes  of  oxygen.  Cuprous  acetjlide  is  an  ex- 
plosive body.  It  is  sometimes  formed  in  brass  gas- 
pipes,  and  has  been  the  cause  of  fatal  accidents. 

Chlorine  acts  upon  acetylene  with  extreme  energy; 
there  is  often  detonation  accompanied  by  light.  On 
moderating  the  action  the  compound  C2H2C12  can 
be  obtained,  which,  as  well  as  the  body  C2H2C14, 
can  also  be  prepared  by  the  action  of  antimonic  chlo- 
ride upon  acetylene. 

As  acetylene  is  not  uncommonly  studied  in  con- 
nection with  inorganic  compounds,  a  more  detailed  ac- 
count of  this  hydrocarbide  need  not  be  given  here. 

Acetylene  is  the  prototype  of  a  homologous  series 
of  hydrocarbides,  of  which  the  general  formula  is, 


The  following  members  of  this  series  are  known 

Allylene,     -  -    C3  H4 

Crotonylene,  -                          C4  H6 

Valerylene,  -     C5  H8 

Rutylene,  C10H18 

Benzylene,  -                     C15H28. 


ETHYLENE.  21 


SECOND  SEKIES. 

General  formula,  CnH2n. 

ETHYLENE. 

Synonyms:  Elayl,  Olcfiant  gas. 

Formula  C2  H4 

Sp.  Gr.  0.97.    Molecular  weight,  28. 

This  gas,  for  no  good  reason  other  than  custom,  is 
always  studied  in  inorganic  chemistry,  usually  in  con- 
nection with  the  consideration  of  illuminating  gas,  of 
which,  with  methane,  it  forms  a  prominent  constit- 
uent. 

Ethylene  is  the  type  of  a  class  of  homologous  hydro- 
carbides,  of  which  the  general  formula  is: 

\Jn    -Lion. 


Each  member  of  the  series  is  related  to  an  alcohol 
from  which  it  may  be  obtained  on  treatment  with 
bodies  having  a  great  affinity  for  water,  as  sulphuric 
acid  or  zinc  chloride. 


22  ORGANIC     CHEMISTRY. 

We  note  the  following  members  of  this  series  : 

Ethylene,  -  -    C2  H4 

Propylene,       -  C3  H6 

Butylene,   -  -    C4  H8 

Amylene,  C5  H10 

Hexylene,  -    C6  H12 

Heptylene,      -  C7  H14 

Octylene,    -  -    C8  H16 

Nonylene,       -  C9  H18 

Paramylene,  -    C 1 0  H  2  0 

Cetene,  -  C^H^ 

Duodecylene,  -                 -     ^i2H24 
Tridecylene,  (Paraffin?)*         C13H26 

Tetradecylene,  C14H28. 

*A.  G.  Pouchet(66— [3]  4—868)  has  prepared  from  paraffin,  by 
oxydation  with  nitric  acid,  paraffin  acid,  C^EUsOa,  from  which 
he  deduces  C24H50  as  the  formula  for  paraffin. 


METHANE. 


THIED  SEEIES. 

General  formula,  CnH^n^r 
METHANE. 

Discovered  by  Yolta  in  1778. 

Synonyms;  Methyl  hydride,  Marsh  gas,  Formene. 

Formula  CH4or  CH3,  H. 

Sp.  Gr.  0.559.    Molecular  weight,  16. 

Permanent  gas,  not  liquifiable,  neutral. 

Not  discussed  in  detail  here  for  the  same  reasons  as 
givun  under  Ethylene. 

Methane  is  the  first  member  of  the  following  very 
important  homologous  series: 

C  H4         methyl  hydride,  or  methane. 


C.H, 

ethyl 

a 

"  ethane. 

CSH8 

propyl 

<.(, 

"  propane. 

c4ri10 

butyl 

a 

"  butane. 

C5  H12 

amyl 

a 

"  amane. 

C6H14 

hexyl 

a 

"  hexane. 

C7H16 

heptyl 

a 

"  heptane. 

C8II18 

octyl 

tt 

"  octane. 

C9  H-20 

nomyl 

tt 

"  nonane. 

CioHa 

decyl 

tt 

"  decane. 

CnH24 

undecyl 

a 

"  undecan< 

Ci2H26 

bidecyl 

tt 

"  bidecane 

24 


ORGANIC    CHEMISTRY. 


tridecyl      "         "  tridecaiie. 
tetradecyl  "         "  tetradecane. 
CisHgj        pentadecyl"        u  pentadecane. 
C16H34        hexadecyl  "        "  liexadecane. 
Nearly  all  the  members  of  this  series  have  been 
found  in  American  petroleum,  mixed  with  members 
of  the  preceding,  or  ethylene,  series. 

Crude  petroleum,  refined  by  fractional  distillation, 
is  still  a  mixture  of  various  hydrocarbons. 

The  commercial  names  given  to  the  products  sep- 
arated at  the  different  boiling  points,  do  not  appertain 
to  chemical  compounds,  or  bodies  having  a  definite 
composition. 

Subjoined  is  a  table  based  on  Dr.  C.  F.  Chandler's 
Heport  on  Petroleum,  (100 — '72-41)  showing  the 

PRODUCTS  OF  THE  DISTILLATION  OF  CRUDE  PETROLEUM.* 


NAME. 

PERCFNTAGE 
YIELUED. 

SPECIFIC 
GKAVITY. 

BOILING 
POINT. 

CHIEF  USES. 

Cymogene  
Rhigolene  

.625 

0°C. 

18.3 

I  Generally   uncondcnsed  —  used    in 
1     ice  machines. 
j  Condensed  by  ice  and  salt—  used  as 

Gasolene  

l1/^ 

.665 

48.8 

(     an  anaesthetic. 
Used  in  making  "air-gas." 

C  Naphtha  
B  Naphtha 

(,0" 

.706 
724 

82.2 
104  4 

{Used  for  oil-cloths,  cleaning,  adul- 
teratin0'  kerosene,  etc.  For  paints 

A  Naphtha  
Benzine 

'" 

.743 

148.8 

and  varnishes, 
Used  to  adulterate  kerosene  oil. 

Kerosene  oil  
Mineral  sperm  
Lubricating  oil  — 
Paraffin  

55 

19* 

.804 
.817 
.833 
Solid. 

176.6 
218.3 
301.6 

Ordinary  oil  for  lamps. 

Lubricating  machinery. 
Manufacture  of  candles. 

*Rc-arrangedfrom  Dr.  C.  F.  Chandler's  Report  on  Petroleum,  presented  to 
the  Board  of  Health,  of  the  City  of  New  York,  1870. 


METHANE.  25 

UNSAFE    KEEOSENE. 

Many  accidents  occur  by  explosion  of  lamps,  when 
kerosene  oil  contains  too  much  of  the  lighter  oils,  ben- 
zine and  naphtha.  This  makes  the  oil  too  readily  in- 
flammable, for  the  lighter  oils  are  driven  out  by  heat- 
ing (as  when  a  lamp  or  kerosene  stove  is  burning),  and 
their  vapors  mixed  with  the  oxygen  of  the  air  form  a 
dangerous  explosive  mixture.  There  is  a  law  requir- 
ing manufacturers  to  keep  kerosene  oil  free  from  these 
lighter  oils,  unfortunately  not  always  faithfully  en- 
forced. 

The  temperature  at  which  kerosene,  on  heating  in 
an  open  vessel,  emits  vapors  which  readily  catch  fire 
on  approaching  a  burning  body,  is  called,  technically, 
the  "  flash  point/'  and  that  at  which  the  kerosene  itself 
inflames  is  called  the  ''burning  point." 

FOSSIL  KESINS,  AND  BITUMEN. 

These  substances  include  amber,  re  tin  asphalt,  as- 
phalt, retinite,  and  many  other  allied  bodies  which  are 
chiefly  contained  in  the  tertiary  strata.  In  many  in- 
stances they  are  the  products  of  the  action  of  an  ele- 
vated temperature  upon  vegetable  bodies;  and  when 
this  is  the  case,  they  form  irregular  deposits  which  im- 
pregnate the  strata  around.  In  many  cases  the  bitu- 
mens occur  in  regular  beds,  which  appear  to  have  been 
formed  in  a  manner  similar  to  the  deposits  of  true  coal. 

Certain  important  building  stones  have  been  found 
to  be  more  or  less  impregnated  with  bitumen. 

Such  is  the  limestone  obtained  at  the  artesian  well 


26  ORGANIC    CHEMISTRY. 

quarry  in  the  city  of  Chicago,  and  the  celebrated 
Buena  Yista,  (Ohio,)  sandstone  used  extensively  in 
Cincinnati;  also  employed  at  Chicago  in  various 
prominent  public  buildings,  as  the  post-office  and 
Chamber  of  Commerce.  The  author,  in  making  a 
chemical  examination  of  the  latter  stone  for  the 
United  States  Treasury  Department,  found  it  to  con- 
tain 2.3  per  cent,  bituminous  matter. 


BENZOL.  27 


FOURTH  SERIES. 

General  formula  Cn  H-2n— 6. 

BENZOL. 

» 

;  Benzene,  Benzine. 
Formula  C,jH6. 

Sp.  Gr.  0.88.    Molecular  weight,  78. 
Sp.  Gr.  of  vapor  2.70. 
Density "      "          39. 
Solid  at  4°.    Boils  at  80.5° 

Benzol  is  obtained,  with  acetylene  and  ethylene,  in 
the  decomposition  of  organic  substances  by  heat, 
and  its  production  is  especially  favored  when  the 
temperature  is  kept  at  a  high  point  for  some  time. 

Ethylene  and  methane  form  at  a  tolerably  low 
temperature.  Acetylene,  which  is  richer  in  carbon, 
is  produced  at  a  higher  temperature.  Benzol  and 
especially  napthalin,  being  still  more  carbonaceous, 
are  formed  at  an  extremely  high  temperature. 

Berthelot  has  prepared  benzol  synthetically  by  con- 
ducting methane  tribromide,  CHBr3,  over  red-hot 
copper : 

6(CHBr3)+9Cu=C6H6-f-9CuBr2 

Benzol  may  be  considered  as  condensed  acetylene: 


28  ORGANIC     CHEMISTRY 

Originally,  banzol  was  prepared  by  a  process  analo- 
gous to  that  which  furnishes  methane,  i.  £.,  by  distill- 
ing benzoic  acid  with  lime, 


C7H602+CaO  =  Ca  C  O5+C6H 


At  present  it  is  obtained  in  immense  quantities  from 
the  tar  which  is  formed  as  an  accessory  product  in  the 
manufacture  of  illuminating  gas. 

At  the  high  temperature  of  the  gas-retort  other  pro- 
ducts, homologous  with  benzine,  are  formed  as  well; 
viz.: 

Toluene  C7  H8      boils  at  110° 

Xylene  C8  H10       "       "  139° 

Cumene  C9  H13       "      "  165° 

Cymeue  C10H14       "       "  180° 

and  other  hydrocarb ides,  as  napthalin  C10H8,  anthra- 
cene, also  various  sulphur  compounds,  notably  carbon 
bisulphide;  several  oxygenated  compounds,  as  phenol 
C6H6O,  cresylol  07H8O  ;  nitrogenous  compounds, 
as  aniline  C6H7N,  and  various  members  of  its 
homologous  series. 

Benzol  is  a  colorless,  neutral  liquid,  with  a  specific 
gravity  of  0.89,  almost  insoluble  in  water  but  soluble 
in  alcohol  and  ether. 

It  dissolves  sulphur,  phosphorus,  iodine,  the  differ- 
ent resins,  and  fatty  substances ;  this  latter  property 
causes  it  to  be  employed  similarly  with  commercial 
"  benzine"  for  cleansing  purposes.  Care  must  be  taken 
to  rub  with  a  piece  of  cloth  having  an  open  texture, 


29 


that  it  may  remove  the  benzol  by  absorption,  without 
which  the  spot  would  reappear  after  evaporation  of  the 
solvent. 

Benzol  burns  with  a  fuliginous  flame.  Nascent 
oxygen  gives  with  it  various  products,  and  notably 
oxalic  acid  and  carbon  dioxide. 

Chlorine  and  bromine  yield  crystalline  compounds 
with  benzol.  Benzol  is  the  simplest  member  of  a 
group  of  bodies  known  as  the  aromatic  compounds,  of 
which  we  shall  proceed  to  describe  some  of  the  more 
important. 

For  distinguishing  benzol  from  the  benzine  of  com- 
merce, which  is  made  from  petroleum,  Brandberg 
recommends  to  place  a  small  piece  of  pitch,  in  a  test 
tube,  and  pour  over  it  some  of  the  substance  to  be  ex- 
amined. Benzol  will  immediately  dissolve  the  pitch 
to  a  tar-like  mass,  while  benzine  will  scarcely  be  col- 
ored. 


This  body  is  obtained  by  treating  benzol  with  fuming 
nitric  acid. 

C.H.+HNO.-  C6H5(N02)+H60. 

Nitro-benzol  is  a  yellowish  oil,  crystallizing  at  37°, 
has  a  sweet  taste  and  an  odor  which  has  led  to  its  use 
in  perfumery  under  the  name  of  essence  of  mirbane. 
Taken  internally  it  acts  as  a  poison. 

On  treatment  of  nitro-benzol  with  nascent  hydrogen, 
hydrogen  sulphide,  or  other  reducing  agent,  we  obtain 


30  ORGANIC    CHEMISTKY. 

aniline,  which  is  a  colorless  liquid,  boiling  at  182°. 
It  does  not  act  upon  litmus,  yet  combines  with  the 
acids,  forming  crystallizable  compounds. 

Aniline  gives  with  chlorine,  bromine  and  nitric  acid 
products  of  substitution  which  are  very  numerous  and 
well  defined.  It  reacts  upon  the  iodides  of  methyl, 
ethyl,  etc.,  forming  the  corresponding  amines,  or  bodies 
constructed  on  the  type  of  ammonia,  having  one  or 
'more  of  the  hydrogen  atoms  replaced  by  an  organic 
compound  radicle: 

(  C.H. 
-      Aniline  C6H,N  =  N  {  H 

IH 

(C6H5 

Methylaniline  CTH9N  =  N  \  0  H3 

H 


Ethylmethylaniline          C9H13N  « 


CH 
CH 


.. 


C6H5  or,  when  free,  (C6H5)2,  is  the  radicle  phenyl, 
hence  aniline  is  properly  phenylamine. 

Aniline  has,  during  the  last  score  of  years,  acquired 
great  importance,  as,  under  the  influence  of  oxydizing 
bodies,  it  forms  most  remarkable  tinctorial  com- 
pounds. 

If  a  small  quantity  of  aniline  is  added  to  a  solution 
of  chloride  of  lime,  the  liquid  is  colored  violet,  which 
color  disappears  iir  a  few  moments.  In  1858,  Perkins 
obtained,  by  the  action  of  potassium  bichromate  and 
sulphuric  acid,  a  beautiful  purple,  which  is  known  in 


BENZOL.  31 

commerce  as  mauve.  Shortly  after,  Yerguin  obtained 
a  magnificent  red  coloring  matter  on  heating  aniline 
with  tin  dichloride. 

This  substance,  known  under  the  names  of  aniline- 
redy  fuchsin,  magenta,  etc.,  is  now  very  economi- 
cally obtained  with  arsenic  oxide  in  place  of  the  tin 
dichloride,  which  is  reduced  to  arsenous  oxide  by  the 
reaction. 

Hoffmann  has  shown  that  aniline-red  is  a  salt  of  a 
colorless  base,  which  he  calls  rosanilirie;  this  substance 
has  the  formula  C^Etl^O,  or  C^H^N^H^O. 

In  the  past  few  years  there  have  been  produced 
green,  yellow  and  black  colors,  all  originating  from 
aniline.  These  substances  dissolve  in  alcohol,  and  dye 
wool  and  silk  without  in  any  way  weakening  the  fabric. 
They  have  a  magnificent  lustre,  but  their  permanency 
is  not  of  the  highest  grade. 

The  consumption  of  aniline  for  dyeing  has  now  come 
to  something  enormous,  amounting  in  Germany  alone 
to  over  15,000  tons  per  annum. 

The  aniline  colors  are  employed  in  injecting  tissues 
for  microscopic  preparations. 

For  a  fuller  account  of  the  aniline  colors,  a  larger 
work  should  be  consulted. 

The  history  of  aniline  affords  one  of  the  most  re- 
markable instances  of  the  value  of  scientific  chemical 
research,  when  perseveringly  and  skillfully  applied, 
for  at  first  few  substances  seemed  to  promise  less; 
and  the  gigantic  manufacturing  industry  at  present 
connected  with  this  compound,  in  its  applications  as  a, 


32  ORGANIC     CHEMISTRY. 

tinctorial  agent,  offers  a  singular  contrast  to  the  early 
experiments  upon  this  body,  when  a  lew  ounces  fur- 
nished a  supply  which  exceeded  the  most  sanguine  ex- 
pectations of  the  early  discoverers  of  this  body. 

PHENOL,  C6H50. 
Synonyms:  Hydrate-of  phenyl,  carbolic  acid  or  phenic  acid- 

It  occurs  in  castoreum,  though  usually  procured  from 
the  portions  of  coal-tar  distilling  over  between  170° 
and  195°.  They  are  agitated  with  caustic  soda, 
water  added  to  separate  the  insoluble  oils,  and  the 
phenol  dissolved  in  the  alkali  is  liberated  as  a  crys- 
talline mass,  on  decomposing  the  potassium  compound 
with  hydrochloric  acid. 

Salicylic  acid,  distilled  with  an  excess  of  lime,  also 
furnishes  phenol; 


C7H603  +  CaO  =  CaC03  + 

Ifphenyl-sulphuricacid,    Vr5  j-  SO4,  obtained  by  di- 

rect action  of  sulphuric  acid  upon  phenol,  is  heated 
with  potassium  hydrate  to  about  300°,  potassic  phenol 
C6H5KO  is  obtained.  Phenol  is  therefore  obtained 
from  benzol  under  the  same  conditions  as  alcohol  is 
obtained  from  ethylene,  the  corresponding  hydro- 
carbide. 

Phenol  crystallizes  in  handsome  needles,  fusible  at 
34°  and  boiling  at  188°.     It  is  little  soluble  in  water, 


PHENOL.  33 

very  soluble  in  alcohol  and  ether.  Phenol  furnishes 
with  chlorine,  bromine  and  iodine  numerous  substitu- 
tion products. 

Phenol  lias  come,  like  alcohol,  to  have  a  generic 
signification,  there  being  a  number  of  analogous  com- 
pounds, though  only  this,  the  ordinary  phenol,  is  an 
important  body.  Heated  with  concentrated  nitric 
acid,  it  furnishes  yellow,  very  bitter,  crystals  of  the 
body  known  as 

PICKIC  or  CARBAZOTIC  ACID. 

Picric  acid  is  also  formed  when  silk,  benzoin,  aloes, 
indigo,  etc.  ,  are  treated  with  nitric  acid. 

Tiiis  acid  is  very  largely  used  in  dyeing,  either  di- 
rectly to  produce  a  yellow  color,  or,  combined  with  in- 
digo, to  produce  a  green. 

Phenol,  though  called  carbolic  acid,  does  not  decom- 
pose the  carbonates,  or  combine  with  the  metals  to 
form  true  salts.  Phenol  dissolves  in  sulphuric  acid 
without  coloration,  if  pure,  and  forms  phenyl-sulphuric 
acid  or  sulpho-carbolic  acid 


H 

which  gives  definite  salts  with  the  metals.  One  of 
these,  the  phenyl-sulphate  or  sulpho-carbolate  of  so- 
dium KaC6H6SO4,  is  claimed  to  have  valuable  proper- 
ties as  a  prophy  lactic  against  scarlet  fever. 

Phenol  gives  certain  reactions  of  the  alcohols  ;    this 


34  ORGANIC    CHEMISTRY. 

somewhat  explains  the  origin  of  the  name  given  it  by 
Berthelot.  This  body  is  the  type  of  a  class  of  com- 
pounds which  contains: 

Cresylol  obtained  from  creosote  C7  H8  O 

Phlorylol      «  "          "  C8  H10O 

Thymol         "         u       essence  of  thyme  C10HUO. 

PHYSIOLOGICAL  ACTION  OF  PHEXOL. 

Phenol  attacks  the  skin,  producing  a  white  stain. 
It  coagulates  albumen  and  is  employed  with  great 
success  as  an  antiseptic  and  disinfectant.  It  is  used 
externally  in  a  diluted  state  to  dress  wounds  which 
suppurate,  also  in  many  surgical  cases. 

It  is  sometimes  used  internally.  Large  doses  of  it 
are  poisonous.  Carbonate  and  especially  saccharate  of 
calcium  are  considered  as  antidotes  for  phenol.  Grace 
Calvert  has  announced  that  olive  or  almond  oil  is  a 
still  better  antidote. 


OIL    OF    TURPENTINE.  35 


FIFTH  SEEIES. 

General  Formula,  Cn  Hgn—t. 

«» 

ESSENCE,     OR     OIL     OF    TURPENTINE. 


Formula 

Density  of  vapor  compared  with  air  4.7. 

Molecular  weight,  136. 

Boils  at  160. 

Turpentine  is  extracted  from  several  varieties  of  the 
family  of  conifera,  notably  from  the  pine,  fir  and 
larch. 

The  products  vary  somewhat  with  the  nature  of  the 
tree,  but  they  have  many  common  characteristics; 
their  composition  is  the  same,  their  density  is  nearly 
identical  and  their  boiling  point  very  nearly  so.  Their 
rotary  action  on  the  solar  ray  varies  largely. 

Isomeric  carbides  are  found  in  other  families  of 
plants,  in  the  aurantiacecB  family  for  instance,  as  the 
lemons  and  oranges.  These  contain  carbides  very  dif- 
ferent, as  evidenced  by  their  odors  and  other  physical 
properties,  also  different  in  certain  chemical  relations, 
yet  having  the  same  composition  as  oil  of  turpentine. 
There  are  also  various  polymers  of  this  carbide. 

This  entire  series  of  hydrocarbons  can  be  divided 
into  three  groups.  The  first  contains  carbides  having 


36  OKGANIC     CHEMISTRY. 


the  formula  C10H16,  their  boiling  points  being  be 

500°,  and 

including  : 

Density. 

Boiling  at 

Oil  of  turpentine, 

0.86 

157°  to  160°. 

a 

cloves, 

0.92 

140°    "145°. 

it 

lemon, 

0.85 

170°    "  175°. 

»< 

orange, 

0.83 

175°    "  180°. 

a 

juniper, 

0.84 

about  160°. 

a 

bergamot, 

0.85 

"      183°. 

u 

pepper, 

O.S6 

"      167°. 

a 

elemi, 

0.85 

"      180°. 

The  carbides  of  the  second  group  have  the  formula 
their  boiling  is  above  200°,  they  are  : 

Oil  of  copaiva,          0.91  245°. 

"      cubebs,  0.93  240°. 

The  third  group  contains  the  non-volatile  carbides, 

such  as 

Density 

Caoutchouc,     -  0.92. 

Gutta-percha,  -     0.98. 

The  rotary  power,  constant  for  each,  varies  with  the 
different  species. 

French  oil  of  turpentine  causes  the  plane  of  polar- 
ization to  deviate  to  the  left;  the  American  variety 
turns  it  13°  to  tke  right;  oil  of  lemon  causes  a  devia- 
tion of  50°  to  the  right;  in  the  case  of  essence  of 
elemi  the  deviation  amounts  to  100°.  Some  of  the 


OIL    OF    TURPENTINE.  37 

essential  oils  of  the  first  group  contain  oxygen  com- 
pounds as  well  as  the  carbohydrid.es. 

The  principal  chemical  differences  between  the 
members  of  the  group  are  the  facility  with  which  they 
are  oxydized  and  their  reaction  with  hydrochloric 
acid.  Essence  of  turpentine  becomes  resinous  rapidly 
when  exposed  to  the  air  and  finally  solidifies.  Es- 
sence of  lemon  becomes  viscid  after  a  considerable 
time.  Hydrochloric  acid  produces,  with  essence  of 
turpentine,  a  liquid  and  a  solid  compound,  having  each 
the  same  composition,  C10H16,  HC1,  which,  after  a 
few  weeks,  becomes  a  dichlorhydride,  (by  some  denomi- 
nated a  dichlorhydrate),  C10H16,2HC1.  Essence  of 
lemon  also  gives  two  dichlorhydrides  at  once,  one 
liquid,  the  other  solid. 

Oil  of  turpentine  may  be  obtained  in  a  pure  state, 
on  distilling  the  commercial  article  in  a  vacuum. 
Thus  obtained,  turpentine  is  colorless,  limpid,  very 
volatile,  and  has  a  characteristic  odor.  It  is  insoluble 
in  water;  very  soluble  in  alcohol  and  ether.  It  burno 
with  a  smoky  flame;  on  exposure  to  the  air  it  oxydize,. 
and  becomes  resinous.  The  same  effect  is  produced 
more  rapidly  with  oxide  of  lead  and  some  other  ox- 
ides which  render  the  oil  siccative  and  suitable  for  use 
in  painting.  J.  M.  Merrick  (100-4-289)  has  noticed 
the  circumstance,  important  in  its  technical  applica- 
tions, that  oil  of  turpentine  attacks  metalic  lead  quite 
strongly;  tin,  on  the  other  hand,  not  at  all.  Turpen- 
tine, if  exposed  to  the  air,  mixed  with  a  solution  of 
indigo,  absorbs  oxygen  and  transfers  it  to  the  indigo,. 


38  OKGANIC     CHEMISTRY. 

which  loses  its  color,  yielding  a  product  of  oxydation 
called  isatin.  Under  these  circumstances,  the  turpen- 
tine does  not  change,  and  a  given  quantity  of  the  es- 
sence can  absorb  several  hundred  times  its  volume  of 
oxygen,  and  oxydize  an  indefinite  quantity  of  indigo. 
This  oxygen  is  probably  the  active  modification,  or 
ozone.  Heated  to  300°  in  a  hermetically  sealed  tube, 
it  changes  into  two  products,  one,  isomeric,  called  iso- 
turpentine,  which  boils  at  1YY°,  and  which  exerts  a 
rotatory  power  of  10°  to  15°  to  the  left;  the  other,  a 
polymer  called  meta-terebenthene,  C^H^  boiling  at 
360°. 

OTHER  SERIES  OF  HYDROCARBIDES. 

Cinnamene  C8H8  is  a  very  refractive  liquid  with 
a  density  of  0.924,  boiling  at  146°.  Styrol  which 
is  produced  from  storax  is  converted  at  205°,  into  a 
polymeric  solid,  termed  Meta-styrol  or  Draconyl.  If 
styrol  is  made  to  act  upon  acetylene,  or  ethylene,  at 
a  red  heat,  there  is  obtained  the  very  important  hydro- 
carbide  naphthalin  Ci0H8.  This  is  a  body  crystalliz- 
able  in  very  handsome  plates,  and  is  ordinarily 
obtained  from  coal  tar  by  distillation  between  200° 
and  300°;  heavy  oils  pass  over,  out  of  which  naphtha- 
lin crystallizes;  on  cooling,  the  mass  is  pressed  and 
purified  by  sublimation.  It  fuses  at  79°  and  distils  at 
220°. 

Naphthalin  is  associated  in  coal  tar  with  a  hydro- 
carbide,  beautifully  crystallizing  in  long  needles,  fus- 
ing at  93°  and  boiling  at  285°.  This  is  acenaphtene 


ALIZARIN.  39 

C12H10.  Another  hydrocarbide  is  also  found  in  this  tar, 
anthracene.  Its  formula  is  C14H10.  It  forms  very 
diminutive  crystalline  plates  fusing  at  210°  and  boil- 
ing at  360°.  Its  vapor  is  extremely  acrid. 

This  body  has  recently  enabled  chemists  to  repro- 
duce the  coloring  principle  of  madder;  alizarin 
CI4H804.  It  is  obtained  on  oxydizing  anthracene  by 
means  of  a  mixture  of  bichromate  of  potassium  and 
sulphuric  acid,  which  gives  oxy  anthracene  C14H8O2. 
This,  with  fused  potassa,  furnishes  a  combination  of 
potassium  and  alizarin,  from  which  the  latter  is  pre- 
cipitated by  an  acid.  It  has  the  form  of  brilliant 
bronze-colored  needles,  identical  with  natural  alizarin 
obtained  from  madder. 

Alizarin  sublimes  at  215°  and  is  very  stable,  little 
soluble  in  cold  water,  but  readily  soluble  in  boiling 
water.  It  is  easily  dissolved  in  alcohol,  ether  and  car- 
bon bisulphide. 

Its  chemical  character,  not  quite  well  defined  as 
yet,  appears  to  place  it  among  the  phenols.  (See 
page  33.) 

The  artificial  production  of  alizarin  from  anthra- 
cene, thus  furnishing  a  cheap  substitute  for  madder, 
the  chief  dye-stuff  used  in  printing  calicoes,  is  one  of 
the  latest  and  most  noteworthy  triumphs  of  organic 
chemistry.  Thousands  of  acres  of  land  in  Europe, 
especially  in  Alsatia,  now  devoted  to  the  culture  of 
madder,  may  be  restored  to  cereal  or  other  food  agri- 
culture. 

Before  leaving  the  hydrocarbons  proper,  it  should 


40  ORGANIC     CHEMISTRY. 

be  stated  that  compounds  of  carbon  and  hydrogen  of 
extra- terrestrial  origin  have  been  found  in  certain  met- 
eorites, by  J.  Lawrence  Smith.  (80-76-388.) 

CAMPHOB. 

Camphor  is  usually  considered  at  this  point,  0:1  ac- 
count of  its  intimate  relation  to  the  oxydized  essential 
oils  in  composition,  and  to  turpentine  in  many  chemical 
reactions. 

Berthelot  regards  camphor  as  an  aldehyd.  Ivekule 
places  it  among  the  ketones. 

Camphor  exists"  in  various  parts  of  the  Laurus 
camphora.  To  obtain  it,  the  wood  is  finely  divided 
and  heated  with  water  in  a  metallic  vessel,  closed  by  a 
cover  filled  with  straw.  The  camphor  is  condensed  in 
grayish  crystals  on  the  straw,  forming  the  crude  cam- 
phor of  commerce  ;  it  is  afterwards  sublimed  in  a  glass 
retort  as  a  further  purification. 

Camphor  is  a  crystallized  body,  having  a  burning 
taste  and  an  aromatic  odor.  Its  density  is  0.99  at 
10°.  It  is  elastic  and  with  difficulty  pulverized,  which 
can,  however,  be  easily  effected  on  moistening  with  a 
few  drops  of  alcohol.  Water  dissolves  only  about  y^Tr 
part  of  it ;  thrown  upon  pure  water  it  floats  on  the 
surface  with  a  gyratory  motion.  It  is  soluble  in  alco- 
hol, ether,  acetic  acid  and  essential  oils ;  it  is  sublimed 
at  ordinary  temperatures  where  kept  in  close  vessels, 
and  deposits  again  on  the  cooler  side  of  the  recep- 
tacle. 

It  burns  with  a  smoky  flame  and  oxydizes  on  being 


EESINS,  BALSAMS,  .GUM-RESINS.  41 

boiled  with  nitric  acid,  yielding  camphoric  acid 
C10H16O4  which  is  bibasic.  Heated  with  zinc  chloride  or 
anhydrous  phosphoric  acid,  it  furnishes  Cymol  C10H14. 

The  author  found  (1-14:6-73)  that  on  treatment  of 
camphor  with  hypochlorous  acid  he  obtained  the -new 
body,  C10H15C1O,  which  he  denominates  monochlor- 
campJwr\  this,  on  treatment  with  alcoholic  potassium 
hydrate,  yielded  oxy  camphor  C10H16O2 . 

Camphor  is  very  extensively  employed  in  medicine 
and  pharmacy. 

RESINS,    BALSAMS,    GUM-RESINS. 

These  bodies  are  products  of  the  oxidation  of  essen- 
tial or  volatile  oils.  The  name  of  gum-resin  is  applied 
to  those  which  contain  a  gum,  and  balsam  to  those 
which  contain  essential  oils  and  an  acid,  usually  cin- 
nainic  or  benzoic,  in  addition  to  the  resin  which  is 
present  in  both.  A.  B.  Prescott,  the  eminent  au- 
thority on  proximate  analysis,  defines  balsams  as  "  natu- 
ral mixtures  of  volatile  oils  with  their  oxidation  pro- 
ducts,— resins  and  solid  volatile  acids. " 

They  are  substances  more  or  less  colored,  hard  and 
brittle.  They  are  fusible,  non- volatile,  and  burn  with 
a  fuliginous  flame.  They  are  insoluble  in  water,  gen- 
erally soluble  in  alcohol,  ether  and  essential  oils. 

Several  of  them  are  acid.  This  is  the  case  with  the 
most  important  of  them,  as  the  resin  of  the  pine,  called 
colophony,  from  which  three  isomeric  acids  have  been 
obtained — ihepinic,  sylmc,  and  pimaric, 


42  ORGANIC     CHEMISTRY. 

This  resin  constitutes  the  fixed  residue  obtained  on 
distilling  crude  turpentine.  It  is  used  for  preparing 
varnish,  in  soldering,  and  in  certain  combinations  with 
the  alkalies,  called  resin-soaps. 

Subjoined  are  given  the  names  and  the  origin  of  the 
principal  resins,  oleo-resins,  gum-resins  and  balsams. 
With  some,  the  position  assigned  them  in  this  classi- 
fication is  not  definitely  settled. 

EESINS. 

Amber  is  found  in  the  lignites  and  in  the  alluvial 
sands  of  the  Baltic. 

Arnicin,  the  active  principle  of  Arnica  Hoot. 

Cannabin,  the  active  principle  of  Indian  Hemp. 

Castorin,  a  secretion  of  the  Beaver  (Castor). 

Ergotin(?),  the  active  principle  of  Ergot  of  common 
rye. 

Mastic,  a  resinous  exudation  of  the  Mastic,  or  Lent- 
isk  tree. 

Burgundy  Pitch,  an  exudation  of  the  Spruce  Fir, 
Abies  excelsa. 

Pyrethrin,  the  active  principle  of  the  Pellitory  root. 

Rottlerin,  a  cr/stalline  resin  from  Kamala,  the  min- 
ute glands  which  cover  the  capsules  of  Rottlera  tinc- 
toria. 

OLEO  -RESINS. 

Copaiva,  a  resinous  juice  of  the  copaifera  offioinalis 
found  in  Spanish  America. 

Wood-oil,  an  oleo-resin  from  the  Dipterocarpm 
turbinatus. 


RESINS,  BALSAMS,  GUM-EESINS.  43 

Elemi,  an  exudation  of  an  unknown  tree,  (probably 
Cannarium  commune). 

Common  Frankincense,  a  concrete  turpentine  of  the 
P'.nus  tceda. 

Canada  balsam,  the  turpentine  of  the  Balm  of  Gilead 
Fir,  (Abies  balsamea). 

Storax,  from  the  Liquidambar  orientale. 

GUM-RESINS. 

Ammoniacum,  an  exudation  of  the  Dorema  ammo- 
niacum. 

Assafoetida,  a  gum.  resin  obtained  by  incision  from 
the  living  root  of  the  Narthex  assafcetida. 

Gamboge,  obtained  from  the  Garcinia  morella. 

Galbanum,  from  the  galbanum  officinale. 

Myrrh,an  exudation  of  the  jBalsamodendronmyrrha. 

BALSAMS. 

Benzoin,  obtained  from  incisions  of  the  bark  of 
Styrax  benzoin. 

Balsam  of  Peru,  from  the  Myroxylon  Pereiros. 

Balsam  of  Tolu,  obtained  from  incisions  of  the  bark 
of  Myroxylon  tuluifera. 


Caoutchouc  is  the  hardened  juice  of  Ficus  elastic^ 
Jatropha  elastica,  Siphotiia  cahuchu,  and  other  plants. 

Gutta-percha  is  the  concrete  juice  of  the  percTia 
(Malay)  tree  the  Isonandra percha,  a  sapotaceous  plant. 


44  OEGANIC     CHEMISTRY. 


ALCOHOLS. 

GENERAL  DEFINITION  AND  CHARACTERISTICS. 

This  name  is  given  to  a  class  of  neutral  bodies  as 
important  as  they  are  numerous.  Their  essential 
characteristic  is  that  of  reacting  upon  acids  so  as  to 
form  water  and  a  class  of  bodies  called  ethers. 

The  number  of  alcohols  is  very  considerable.  There 
are  several  distinct  varieties  of  alcohol  recognized. 

I.  Those  built   on   the   type  of  one  molecule  of 
water: 

C  H  '  ) 

TT5    \  O,  ethyl  or  common  alcohol. 

II.  On  two  molecules  of  water  : 

O  TT  f  '  } 
2TT4      [-  O2,  ethylene  alcohol  or  glycol. 

III.  On  three  molecules  of  water  : 

O  TT  '  '  '  ) 

I  O3,  glycerine  and  thus  on. 

"8  ) 

They  may  be  defined  as  bodies  built  on  the  type  of 
one  or  more  molecules  of  water  having  one-half  of  the 
hydrogen  replaced  by  a  hydrocarbide  radicle. 

MONATOMIC    ALCOHOLS, 

or  those  formed  on  the  type  of  one  molecule  of  water, 


ALCOHOLS.  45 

of  which  ordinary  alcohol  is  the  best  studied,  are 
characterized  by  the  fact  that  they  contain  one  atom 
of  oxygen  only,  and  that  by  reaction  with  the  mono- 
basic acids  they  form  only  a  single  ether. 

They  in  ay  be  obtained  synthetically,  as  well  as  by 
various  indirect  processes. 

Subjoined  is  a  classified  list  of  the  more  important 
monatomic  alcohols: 

FIRST    SERIES, 

CnH2+20. 

Methyl  alcohol  (wood  spirit),  C  H4  O 
Ethyl  alcohol,  (spirit  of  ,wine)  C2  H6  O 

Propyl  alcohol  C3  H8  O 

Butyl  alcohol,  -     C4H10O 

Amyl  alcohol,  05  H12O 

Setyl  alcohol  -     C6  H14O 

Octyl  alcohol  C8H18O 

Sexdecyl  alcohol    -  -     C^ED^O 

Ceryl  alcohol  C27H56O 

Myricyl  alcohol    -  C^H^  O 

SECOND    SERIES, 

CnII2nO. 

Yinyl  alcohol  C2  H4  O 

Allyl  alcohol      -  C3  H6  O 

THIRD    SERIES, 

*  Cn  H2n_2  O. 
Eorneol  alcohol  C10H18O 


46  ORGANIC     CHEMISTRY. 

FOURTH     SERIES, 


Benzyl  alcohol  C7  H8  O 

Xylyl  alcohol      -  08  H10O 

Curaol  alcohol  C9  H12O 

Cjmol  alcohol      -  -  C10HUO 

FIFTH   SERIES, 

OH       O 

^n-^Sn—  8^- 

Cinnyl  alcohol  C9  H10O 

Cholesteryl  alcohol  -   C26  H44O 

MONATOMIC  ALCOHOLS  HAVING  THE  GENERAL  FORMULA, 


METHYL    ALCOHOL,    OR   WOOD-SPIRIT. 
CH40  =  °^3  |  O. 

This  substance  is  found  in  the  liquid  obtained  on 
distilling  wood.  The  distillate  contains  in  addition, 
water,  acetic  acid,  tar,  and  various  oils.  In  order  to 
extract  the  methyl  alcohol,  it  is  again  distilled  and 
that  portion  which  passes  over  at  90°  is  collected  ;  this 
is  diluted  with  water,  the  oil  which  precipitates  sepa- 
rated, and  the  liquid  agitated  for  a  considerable  time 
with  olive  oil.  This  oil  is  then  removed,  the  liquid 
redistilled  several  times  and  only  that  portion  collected 
which  passes  over  above  70°.  On  being  again 


ALCOHOLS.  47 

distilled  with  calcium  chloride  ife  furnishes  methyl  al- 
cohol, nearly  pure,  boiling  at  66.5°. 

There  are  other  methods  of  rectifying  besides  the 
one  here  given. 

This  body  possesses  most  of  the  general  properties 
of  ordinary  alcohol.  Under  the  action  of  the  oxides  it 
furnishes  an  aldehyd  and  formic  acid. 

With  the  acids  it  produces  ethers;  viz.,  with 

CII  / 
hydrochloric  acid,  methyl  chloride,  CH3C1=  ^3  j- ; 

with  acetic  acid, 

methyl  acetic  ether,  C3H6O2=g  ^3O  j.  O. 

CHLOROFORM,    CIIC18 . 

Methyl  chloride  produces  with  chlorine  a  regular 
series  of  products  of  substitution.  One  of  these  terms, 
CHC13,  is  the  very  important  body,  chloroform,  dis- 
covered in  1831  by  Soubeiran  and  Liebig. 

To  prepare  this  compound,  40  litres  of  water,  5  kilos 
of  recently  slacked  lime,  and  10  kilos  of  chloride  of 
lime  are  heated  to  40°;  1500  grams  of  90  per  cent, 
alcohol  are  then  added  and  the  retort  luted  with  clay. 

It  is  now  heated  for  a  moment  to  the  boiling  point 
and  the  fire  then  at  once  slackened. 

The  ebullition  having  ceased  there  will  be  found  two 
layers  in  the  receiver.  The  upper  layer  is  formed  of 
water  and  alcohol,  the  lower  one  is  chloroform  nearly 
pure.  The  latter  is  washed  with  water,  agitated  with 
a  dilute  solution  of  potassium  carbonate,  or  with  fused 


48  ORGANIC     CHEMISTRY. 

calcium  chloride  for  twenty-four  hours,  and  distilled 
to  four-fifths. 

Chloroform  is  a  colorless  liquid.  When  first  pre- 
pared it  has  a  sweetish  penetrating  taste,  and  an  agree- 
able, ethereal  odor. 

Its  density  is  1.48;  it  boils  at  60.5°,  is  soluble  in 
alcohol  and  ether  and  difficultly  so  in  water. 

It  burns,  though  not  readily;  its  flame  ha  vino-  a 
green  margin.  It  dissolves  iodine,  sulphur,  phos- 
phorus, fatty  substances  and  resins. 

An  alcoholic  solution  of  potassa  decomposes  it  into 
chloride  and  formiate : 

CHC13  -f  4KHO  —  3KC1  -f  CHKO2  -f  2H,O. 
PHYSIOLOGICAL  ACTION. 

Chloroform  is  at  present  very  generally  used  as  an 
anesthetic.  Opinions  as  to  its  manner  of  acting  are 
divided.  Formerly  it  was  thought  that  the  insensi- 
bility produced  was  the  commencement  of  asphyxia. 
Since  then  it  has  been  ascertained  that  the  heart,  in 
case  of  poisoning  by  chloroform,  immediately  loses  all 
powerof  contraction^  and  it  is  now  generally  admitted 
that  paralysis  of  the  muscles  and  nerves  of  the  heart  is 
produced. 

As  the  vapor  of  chloroform  is  very  dense,  care  should 
be  taken  that  in  its  use,  access  of  air  to  the  lungs  be 
not  wholly  prevented,  or  serious  consequences  may  re- 
sult. Probably  the  fatal  accidents  that  have  occurred 


ALCOHOLS.  49 

may,  in  some  instances  at  least,  be  attributed  to  lack 
of  care  in  this  regard. 

It  is  of  great  importance  that  the  chloroform  used 
should  be  quite  pure.  In  some  cases  it  has  been  found 
to  have  undergone  spontaneous  decomposition  after 
exposure  to  a  strong  light.  It  ought  to  communicate 
no  color  to  oil  of  vitriol  when  agitated  with  it.  The 
liquid  itself  should  be  free  from  color  or  any  chlorous 
odor.  When  a  few  drops  are  allowed  to  evaporate  on 
the  hand  no  unpleasant  odor  should  remain. 

Shuttleworth  (100,  4,  339)  states  that  partially  de- 
composed chloroform  can  be  rectified  by  agitating  it 
with  a  solution  of  sodium  hypo-sulphite. 


OKDESTAEY  ALCOHOL. 

ETHYLIC,  OR  YINIC  ALCOHOL. 

Formula:  C->H6O. 
Density  of  vapor  20. 
Density  .81. 
Boils  at  78.4o. 
Cannot  be  solidified. 

It  is  prepared  by  the  fermentation  of  saccharine 
liquids  at  a  temperature  of  25°  to  30°,  in  the  presence 
of  a  small  quantity  of  a  ferment.  Cane  sugar  does 
not  directly  become  alcohol  under  the  influence  of  a 
ferment.  It  is  first  transformed  into  two  other  sugars, 
glucose  and  levulose. 


50  ORGANIC     CHEMISTRY. 

C12H22On+  H20 


Glucose.  Levulose. 


In  its  final  fermentation  nearly   all   the  sugar  is 
changed  into  alcohol  and  carbon  dioxide, 


This  equation  accounts  for  the  transformation  of  94 
to  96  per  cent,  of  the  sugar  employed,  but  besides 
alcohol  and  carbon  dioxide,  succinic  acid  is  always 
formed  as  well  as  glycerine,  and  in  most  cases  "  fusel 
oil,"  consisting  chiefly  of  amyl  alcohol. 

Fermentation  is  a  phenomenon  correlative  with  the 
development  and  growth  of  cells  of  the  fungus  Myco- 
derma  (Torula)  cerevisice  which  constitutes  yeast. 
Sometimes  the  sugar  is  furnished  as  a  natural  product 
by  fruits  ;  often  glucose  is  produced  from  the  starch 
of  cereals,  potatoes,  etc.,  and  then  changed  into  alcohol 
afterwards.  Corn  is  the  leading  original  source  in 
this  country. 

Alcohol  obtained  by  fermentation  is  concentrated 
by  distillation.  This  operation  is  performed  in  retorts, 
the  construction  of  which  is  based  upon  a  principle 
developed  by  A.  de  Montpellier,  and  improved  by 
Derosne,  Dubrunfaut  and  others.  The  object  is  to 
prevent  the  distilling  over  of  the  water  with  the  alco- 
hol, and  is  quite  well  accomplished  by  the  improved 
methods  now  employed.  The  details  are  not  suited 
to  the  scope  of  this  work. 

The  application  of  this  rational  method  of  distilling 


ALCOHOLS.  51 

admits  of  obtaining  liquids  containing  up  to  90  per 
cent,  of  alcohol,  but  it  is  difficult  to  go  beyond  that 
point  of  concentration. 

In  order  to  prepare  alcohol  more  concentrated,  sub- 
stances having  a  great  avidity  for  water  must  be  used. 
Calcium  chloride  is  not  suitable,  as  it  unites  with 
the  alcohol.  Anhydrous  sulphate  of  copper,  carbon- 
ate of  potassium  or  quicklime  do  not  produce  absolute 
alcohol.  But  it  is  very  rare  that  perfectly  anhydrous 
alcohol  is  required.  Alcohol  of  97  per  cent,  is  obtained 
in  treating  alcohol  of  85  per  cent,  during  two  days  with 
lime,  or  better,  with  a  sixth  or  seventh  part  of  its  weight 
of  dry  potassium  carbonate,  and  then  distilling.  If  it 
is  desired  to  procure  absolute  alcohol,  very  concen- 
trated alcohol  is  treated  with  caustic  baryta  until  the 
liquid  is  colored  yellow  and  then  distilled. 

Alcohol  in  fresh  bread  made  with  yeast  has  been 
found  by  Bolas  (8-27-271)  to  the  amount  of  .314  per 
cent.  Slices  of  bread  a  week  old  contained  .12  to  .13 
per  cent. 

Absolute  alcohol  is  a  colorless  liquid,  more  limpid 
than  water,  of  an  agreeable  odor  and  a  burning  taste. 
It  boils  at  78.4:°,  is  neutral,  combustible  and  burns 
with  a  flame  but  little  luminous.  It  heats  on  coming 
in  contact  with  water,  and  attracts  the  moisture  of  the 
air  very  rapidly. 

It  contracts  upon  mixing  with  water;  the  max- 
imum of  contraction  takes  place  at  a  temperature  of 
15°  when  52. 3  vol.  of  absolute  alcohol  are  mixed 
with  47.7  vol.  of  water;  instead  100  vol.  one  obtains 


52  .      ORGANIC     CHEMISTRY 

96.3   vol.     At  the  moment  of  admixture  numerous 
air  bubbles  escape  and  the  mixture  becomes  heated. 

The  alcoholic  strength  of  the  liquids  consumed  as 
"beverages  varies  considerably. 


Madeira  wines, 
Malaga         " 
Bordeaux      " 

about            20  per  cent. 
"      14  to  16         " 
5  to  12 

Shine            " 

"      10  to  12 

u 

California     " 

Y 

a 

Cider 

"     2  to  7 

a 

Beer 

"        1  to    8 

a 

Spirits  are  distilled  from  fermented  liquids;  brandy 
from  wine ;  whisky  from  a  mash  of  corn  or  rye  ;  rum 
from  molasses,  etc.  They  contain  abort  50  per  cent, 
of  alcohol. 

The  term  proof  spirits  was  originally  given  to  al- 
cohol sufficiently  strong  to  fire  gunpowder  when 
lighted.  The  strength  of  proof  spirits  now  varies  in 
diiferent  localities,  and  it  would  be  wrell  were  this 
ambiguous  designation  no  longer  employed. 

Alcohol  dissolves  the  caustic  alkalies,  certain  ni- 
trates, chlorides  and  other  salts,  also  various  gases. 
With  some  of  these,  genuine  chemical  combinations 
are  produced,  and  not  mere  solutions;  this  is  the  case 
with  calcium  chloride  and  magnesium  nitrate. 
Alcohol  can  be  mixed  with  ether  in  all  proportions; 
it  dissolves  the  resins,  essential  oils,  and  a  great  num- 
ber of  other  organic  bodies. 

The  chemical  properties  of  alcohol  are  very  inter- 


ALCOHOLS.  53 

esting.  Yapor  of  alcohol  is  decomposed  on  passing 
through  a  tube  heated  to  redness;  hydrogen,  marsh- 
gas,  oxide  of  carbon,  small  quantities  of  naphthalin, 
benzol,  and  phenol  are  formed.  In  presence  of  air 
and  water  it  slowly  oxidizes  and  yields  acid  com- 
pounds. This  action  is  rapid,  if  a  hot  spiral  of  plati- 
num is  placed  in  the  alcoholic  vapor. 

EXPERIMENT. — Place  a  small  platinum  spiral  in  the 
wick  of  an  alcohol  lamp,  light  and  then  blow  out  the 
flame.  It  will  be  seen  that  the  spiral  remains  incan- 
descent. Spongy  platinum  acts  still  more  energetically; 
if  very  concentrated  alcohol  is  poured  drop  by  drop  into 
a  capsule  containing  spongy  platinum,  or  platinum 
black,  it  will  be  seen  to  redden,  fumes  are  produced  and 
an  acid  liquid  is  formed  containing  chiefly  aldehyd 
and  acetic  acid.  The  same  oxidation  occurs  if  diluted 
alcohol  is  exposed  to  the  air  in  the  presence  of  mother  of 
vinegar,  a  cryptogamic  plant,  (Mycoderma  aceti).  In 
fact,  this  is  the  basis  of  the  manufacture  of  wine-vin- 
egar and  alcohol. 

Fuming  nitric  acid  reacts  upon  alcohol  with  ex- 
plosive energy.  Aldehyd  is  formed,  also  acetic  ether, 
nitrous  ether  and  acetic,  formic,  glycollic,  oxalic  and 
carbonic  acids.  Alkaline  hydrates  attack  alcohol  even 
in  the  cold  potassium  acetate  being  the  chief  product 
formed.  If  alcoholic  vapor  is  made  to  pass  over  lime 
heated  to  250°,  hydrogen  gas  and  calcium  acetate 
are  produced;  the  latter  is  decomposed  at  a  more 
elevated  temperature  into  marsh  gas  and  water.  If 
silver  or  mercury  is  dissolved  in  nitric  acid,  and 
90  per  cent,  alcohol  added  to  the  cooled  solutions,  a 


54  ORGANIC    CHEMISTRY. 

lively  ebullition  results,  and  a  crystalline  precipitate  is 
deposited  which  explodes  at  185°,  or  by  percussion. 
This  body  is  the  fulminate  of  silver  or  mercury,  re- 
spectively, which  is  considered  as  derived  from  methyl 
cyanide,  CH3Cy,  by  the  substitution  of  1  molecule  of 
nitryl,  and  of  1  atom  of  mercury,  or  2  of  silver  for  3 
atoms  of  hydrogen.  The  formula  are  C(N02)HgCy; 
C(N02)Ag2Cy. 

Potassium  attacks  absolute  alcohol,  and  is  dissolved 
liberating  hydrogen;  on  cooling,  potassium  ethylate  is 
deposited.  Sodium  acts  in  the  same  manner.  These 
compounds,  if  brought  in  contact  with  water,  regenerate 
alcohol  and  the  respective  alkaline  hydrates. 

Acids  attack  alcohol  and  furnish  compound  ethers, 
which  we  will  study  later.  Ozone,. according  to  A.  W. 
Wright,  (80— 1_3]7— 184)  oxydizes  alcohol  to  acetic  acid. 

PHYSIOLOGICAL  ACTION  OF  ALCOHOL.  USES  OF  AL- 
COHOL.— Alcohol  coagulates  the  blood;  injected  into  the 
veins  it  produces  instantaneous  death.  It  is  a  very 
powerful  poison,  as  are  all  alcohols  of  the  series 
•CnEkn+aO.  Rabuteau  (9—81—631)  has  shown  that 
they  are  more  poisonous  in  proportion  as  their  mole- 
cules are  complex.  Cases  have  been  observed  where  a 
large  dose  of  alcohol  has  caused  death  in  half  an  hour. 

The  worse  than  worthless  character  of  distilled 
liquors  as  beverages  is  no  longer  an  open  question. 
With  regard  to  their  value  as  food  or  medicine,  a  more 
authoritative  or  competent  expression  of  opinion  can- 
not be  desired  than  that  of  the  International  Medical 
Congress,  which  at  its  session  in  Philadelphia  in  1876, 
said: 


ALCOHOLS.  55 

"1.  Alcohol  is  not  shown  to  have  a  definite  food 
value  by  any  of  the  usual  methods  of  chemical  analy- 
sis or  physiological  investigation. 

"  2.  Its  use  as  a  medicine  is  chiefly  that  of  a  cardiac 
stimulant,  and  often  admits  of  substitution. 

"  3.  As  a  medicine,  it  is  not  well  fitted  for  self-pre- 
scription by  the  laity,  and  the  medical  profession  is 
not  accountable  for  such  administration,  or  for  the 
enormous  evils  arising  therefrom. 

"4:.  The  purity  of  alcoholic  liquors  is,  in  general, 
not  as  well  assured  as  that  of  articles  used  for  medicine 
should  be.  The  various  mixtures  when  used  as  medi- 
cine, should  have  definite  and  known  composition,  and 
should  not  be  interchanged  promiscuously." 

The  dissolving  power  of  alcohol  renders  it  very  ser- 
viceable in  the  arts.  Solutions  in  this  menstruum  are 
called  alcoholic  tinctures.  Only  the  purest  alcohol 
ought  to  be  used  in  pharmacy,  though  of  course,  various 
strengths  are  requisite,  as  it  should  be  of  a  degree  to 
suit  the  nature  of  the  matter  to  be  dissolved.  If  the 
substance  to  be  treated  is  a  resin,  or  some  substance 
absolutely  insoluble  in  water,  a  very  concentrated  alco- 
hol is  preferable.  A  weaker  alcohol  is  made  use  of,  if 
the  matter  is  one  that  is  soluble,  both  in  alcohol  and 
water. 

Alcohol  acts  not  only  as  a  solvent,  but  also  as  a  pre- 
ventative  of  decay.  This  is  a  property  which  renders 
it  especially  valuable  in  the  preparation  of  remedies. 


56  ORGANIC    CHEMISTRY. 

AMYL  ALCOHOL. 

C5H120  =  C5Hn  1  Q 
II    [,°- 

Synonyms:     FOUSEL  (OR  FUSEL)  OIL,  POTATO  SPIRIT. 

The  amylic  compounds  derive  their  name  from 
Amylum,  starch,  the  chief  constituent  of  the  potato. 
They  are  formed  in  some  proportion  in  almost  every  in- 
stance of  alcoholic  fermentation  of  sugar.  Ainylic 
alcohol  is  usually  prepared  on  fractionally  redistilling 
the  oil  which  remains  when  the  alcohol,  prepared 
from  potatoes,  barley,  corn,  etc.,  is  distilled.  The  pro- 
duct which  comes  over  at  132°,  is  that  collected. 
Cahours  and  Balard  first  established  the  analogy,  in 
constitution  and  properties,  of  this  compound  with 
ordinary  alcohol.  It  is  a  monatomic  alcohol,  giving 
with  oxidizing  re-agents,  valeric  acid. 


Amylic  alcohol.  Valeric  acid. 

and  with  acids,  compound  ethers,  as 

Chloride  of  amyl,  OsHuCL 

r\  TT         N 

Acetate  of  amyl  or  amyl-acetic  ether,        (/f^Q  !"  ®' 


ALCOHOLS.  57 

MONATOMIC  ALCOHOLS. 

Having  the  general  Formula  CnH2nO. 

ALLYLIC  ALCOHOL,  C3H6O  =  C3H5 

H 

This  is  a  body  giving  the  same  reactions  as  ordinary 
alcohol.  The  radicle  it  contains  is  the  same  as  that 
in  the  triatomic  alcohol,  glycerine.  Among  its  deriva- 
tives there  are  two  which  are  of  considerable  impor- 
tance : 

Allyl  sulphide,  ^5  j.  S. 

Sulpho-cyanide,  P3]V5  [  ^* 

The  former  is  oil  of  garlic;  the  latter  oil  of  mustard. 
OIL  OF  GARLIC  is  prepared  by  the  following  method: 
allylic  alcohol  is  treated  with  phosphorus  iodide  which 
furnishes  allyl  iodide  C3H5I.  This  iodide  is  afterwards 
mixed  with  an  alcoholic  solution  of  potassium  sulphide 
and  the  whole  is  distilled;  the  product  which  passes 
over  is  identical  with  the  essential  oil  obtained  in  dis- 
tilling garlic,onions,  assafoetida,  etc.,  with  water. 

OIL   OF   MUSTARD,   OR   SULPHO-CYANIDE   OF    ALLYL. 

This  body  is  prepared  by  causing  iodide  of  allyl  to 
react  upon  potassium  sulpho-cyanide,  ^  j-  S,  and  may 

be  regarded  as  sulpho-cyanic  acid,    "     !•  S,  having  the 


58  ORGANIC     CHEMISTRY. 

hydrogen  replaced  by  the  radicle  of  allyl  alcohol,  C3H5. 
The  product  which  distills  over  is  an  irritating  liquid 
which  boils  at  145°,  like  the  oil  prepared  from  mus- 
tard directly.  This  substance  may  also  be  obtained 
by  the  action  of  allylic  alcohol  upon  potassium  sul- 
pho-cya:ride.  It  is  likewise  obtained  by  the  fermenta- 
tion of  mustard  seeds. 

Sulpho-cyanide  of  allyl  does  not  exist  already  formed 
in  black  mustard  (Sinapis  nigra\  but  according  to 
Bussy,  its  formation  is  due  to  a  particular  ferment. 

Oil  of  mustard  combines  directly  with  ammonia, 
forming  a  crystalline  substance  called  thiosinnamine, 
C4H8^N"2S,  which,  in  contact  with  mercuric  oxide, 
changes  into  an  alkaloid  called  sinnamine,  of  which 
the  composition  is  C4H6N2-  It  reacts  upon  lead  oxide 
producing  a  substance  called  sinapoline  whose  formula 
is  C7K12N20. 

BORNEO   CAMPHOK,   OR    BO3NEOL    C10Hi8O. 

This  body  exudes  from  the  dryobalanops  camphora 
(Borneo).  It  is  crystalline  and  has  an  odor  between 
that  of  camphor  and  pepper.  It  fuses  at  195°,  and 
boils  at  about  220°.  It  is  dextrogyrate.  Heated  with 
nitric  acid  it  furnishes  common  camphor  C10H6O. 

DIATOMIC    ALCOHOLS  OR  GLYCOLS. 
•  CnH2n+202. 

Ordinary  Glycol,  (C2HJ  —  02—  H2=C2H6  0, 
Propyl  -      (C3H6)  _02-H2=C3H8  Q, 


ALCOHOLS.  59 


Butyl  Glycol,  (C4H8)  -02-HS=C4H100S 

Amyl  (C5H10)-02-H3=C5H1802 

Hexyl       "  (C6HI2)-08-H,=C6H1402 

Octyl  (C8H16)-03-H2=C8H1808. 

TRIATOMIC  ALCOHOLS. 

Glycerine,  (C3H5)-03-H3=C3H8(V 

TETRATOMIC    ALCOHOLS. 

Erythrite,  (C4H6)-04-H4=C4H1004. 

^  OTHER   COMPLEX   ALCOHOLS. 

Glucose  and  its  isomerides,  (C6H6)—  06—  H6  ^C^  206. 
Mannite,  -      (C6H8)-06-H6=C6H1406. 

Dulcite,  (C9H8)-06-H6=C6H1406. 

Quercite,  IT  H  O    -  (CR^^  i 

Pinnite,  f^iiMfVi  T      H2      f 

ORDINARY    GLYCOL. 


The  discovery  of  the  glycols  was  an  event  of 
great  importance.  It  was  achieved  by  Wurtz  in  1856, 
and  the  glycol  of  which  we  are  treating  was  the  first 
discovered. 

In  a  flask  surmounted  by  a  condenser,  two  parts  of 
potassium  or  sodium  acetate,  are  dissolved  in  weak 
alcohol  and  one  part  of  ethylene  bromide  added.  This 


60  ORGANIC    CHEMISTRY. 

mixture  is  heated  in  a  water  bath  as  long  as  the  pre- 
cipitate of  alkaline  bromide  continues  to  form,  care 
being  taken  at  the  same  time  to  keep  the  worm  well 
cooled,  in  "order  that  the  vapors  of  alcohol  may  contin- 
ually flow  back  into  the  flask.  The  alcohol  is  distilled 
off  in  a  water  bath,  and  the  residue  afterwards  also 
distilled  at  a  higher  temperature,  and  that  part  col- 
lected which  passes  over  between  140°  and  200° .  This 
portion  which  contains  monacetic  glycol,  is  heated 
with  a  saturated  solution  of  baryta  until  the  liquid 
acquires  a  strong  alkaline  reaction.  The  excess  of 
baryta  is  removed  by  passing  carbon  dioxide  through 
the  solution  which  is  then  filtered  and  evaporated. 
The  barium  acetate  is  precipitated  completely  by  strong 
alcohol,  and  the  alcohol  subsequently  removed  by  dis- 
tillation. The  retort  is  now  heated  in  an  oil  bath,  and 
that  portion  set  aside  which  boils  above  150° .  This  is 
redistilled  and  the  distillate  between  190°  and  198° 
is  the  product  sought.  Zeller  and  Huefner  have  lately 
(18,  10,270)  obtained  the  purest  glycol  by  simply  heat- 
ing a  solution  of  potassium  carbonate  with  ethylene 
bromide. 

Glycol  is  a  colorless,  odorless  liquid,  somewhat 
viscid  and  having  a  sweetish  taste.  Its  density  is 
1.12;  water  and  alcohol  dissolve  it  in  all  proportions. 
Ether  dissolves  it  with  difficulty. 

It  is  not  oxydized  in  the  air  under  ordinary  con- 
ditions, but  if  dilute  glycol  be  made  to  fall  on  plati- 
num black,  it  becomes  heated  and  is  transformed  into 
gly colic  acid.  Its  equivlence  is  shown  by  the  follow- 


ALCOHOLS.  61 

ing  :    glycol    attacks    sodium    forming  two    sodium 
glycols; 


These  glycols  furnish  two  ethyl  glycols  on  being 
heated  with  ethyl  iodide. 

C2H4    ) 

*  (C2H5) 

Ethyl-glycol.  Diethyl-glycol. 

With  hydrogen  bromide  it  furnishes  two  different 
products  according  to  the  number  of  molecules  of  HBr 
taken. 

CaHA+  HBr  =  C2H5BrO  +  H2O. 

Monobromhydric 
ether. 


CaH602  +  2HBr-C2H4Br+  2H2O. 


Ethylene 
bromide. 


It  is  evident  that  mixed  ethers  may  be  obtained  by 
treating  glycol  not  with  two  molecules  of  the  same 
acid,  but  with  two  molecules  of  different  acids.  Thus 

C  TT 

aceto-chlorhydric  glycol  is  formed  ,p  TT  Q\pf 


62  ORGANIC    CHEMISTRY. 

These  ethers,  in  the  presence  of  alkalies,  are  re- 
formed into  their  respective  acids  and  glycol,  in  the 
same  manner  in  which  ethers  of  ordinary  alcohol 
regenerate  alcohol. 

Monochlorhydric  and  aceto-chlorhydric  glycol  form 
an  exception  to  this  rule  ;  they  form  oxide  of  ethylene 
in  presence  of  alkalies. 

OXIDE  OF  ETHYLENE,   C2H4O, 

a  polymer  of  (C2H4)2O2,  is  related  to  glycol  as  ordinary 
ether  to  alcohol.  It  is  not  obtained  like  the  latter  by  the 
action  of  hydrogen  sulphate  on  the  alcoholic  compound, 
but  is  produced  by  the  action  of  potassa  on  mono- 
chlorhydric  glycol.  A  solution  of  potassa  is  gradually 
poured  into  chlorhydric  glycol  placed  in  a  glass,  or  a 
tubulated  retort. 

KHO  +  C3H5C10  -  KC1  +  H20  +  C8H40. 

The  oxide  of  ethylene  distills  over  with  the  water; 
the  latter  is  absorbed  by  causing  the  vapors  to  pass 
through  a  flask  containing  anhydrous  calcium  chloride, 
and  the  oxide  is  condensed  in  a  receptacle  placed  in  a 
refrigerating  mixture. 

It  is  a  colorless,  ethereal,  fragrant  liquid;  boiling  at 
13°.  Its  density  is  0.89.  Ethylene  oxide  is  very  solu- 
ble in  water,  alcohol  and  ether.  It  burns  with  a  lumin- 
ous flame  and  reduces  silver  salts.  It  has  the  compo- 
sition but  not  the  properties  of  aldehyd,  of  which  it  is 
an  isomeride. 


ALCOHOLS.  63 

Oxide  of  ethylene  is  a  very  remarkable  body.  It 
combines  directly  with  oxygen,  hydrogen,  chlorine  and 
bromine,  also  combines  directly  with  acids,  often  even 
with  the  disengagement  of  heat,  forming  the  ethers  of 
glycol  and  polyethylenic  alcohols.  This  body  is  there- 
fore a  true  non-nitrogenous  basic  oxide. 


64  OKGANIC     CHEMISTRY. 


TEIATOMIC  ALCOHOLS  OR  GLYCERINES. 

ORDINARY  GLYCERINE,  C3H8O3  =°3u5  '  O-  . 

-ti3  ) 

This  body,  discovered  by  Scheele,  in  1779,  and 
called  by  him,  on  account  of  its  sweet  taste,  the  sweet 
principle  of  oils,  has  been  specially  studied  by  Chevreul 
and  by  Pelonze.  Berthelot  discovered  its  real  nature 
and  proved  it  to  be  a  triatomic  alcohol. 

Glycerine  is  prepared  by  decomposing  neutral 
fatty  bodies,  in  the  soap  and  candle  industry  by  alka- 
lies, or  better  still  by  superheated  steam.  (Tilghmaii's 
process.)  It  is  obtained  in  pharmacy,  whenever  lead 
plaster  is  prepared  arid  remains  in  the  water  with 
which  the  latter  is  washed. 

It  is  much  employed  in  pharmacy  and  perfumery 
and  as  a  solvent  for  many  substances.  Crude  glycer- 
ine may  be  purified  by  boiling  with  animal  charcoal 
and  filtering  before  being  evaporated  to  the  required 
consistency.  The  best  process  consists  in  distilling  the 
crude  condensed  glycerine  in  a  current  of  steam.  Pas- 
teur has  shown  that  glycerine  is  produced  in  a  very 
small  quantity  in  alcoholic  fermentation.  We  owe  to 
Wurtz,  a  remarkable  synthetical  reproduction  ofglycer_ 
ine.  Pi  opylene  C3H6  furnishes  an  iodide  C3H5I,  called 
iodide  of  allyl.  This  body  produces  with  bromine  the 


ALCOHOLS.  65 

compound    C3H5Br3  which,    treated   with  potassa,   or 
oxide  of  silver,  yields  glycerine. 

C3H5Br3+3KHO  =  3  KBr.+C8H8O8 

Glycerine. 

Glycerine  is  a  syrupy  liquid,  colorless,  of  a  sweetish 
taste  and  destitute  of  odor;  its  density  is  1.28  at  15°. 
Sarg  has  obtained  crystals  of  glycerine,  whose  angles 
have  been  measured  by  Victor  Lang  (2-152-637). 
They  are  rhombic  in  form  and  very  deliquescent.  Glyc- 
erine is  soluble  in  alcohol  and  water  in  all  propor- 
tions; it  is  not  dissolved  by  ether.  It  dissolves  alka- 
lies, alkaline  sulphates,  chlorides  and  nitrates,  copper 
.sulphate,  silver  nitrate  and  many  other  salts. 

Glycerine  distills  at  280°,  but  is  thereby  partially 
decomposed.  It  may,  however,  be  distilled  in  a 
vacuum  without  change.  It  is  decomposed  at  a  tem- 
perature above  300°,  and  oils,  inflammable  gases, 
carbon  dioxide,  and  a  product  very  irritating  to  the 
eyes,  called  acrolein*  acrylic  aldehyd,  are  formed; 
this  last  substance  may  be  obtained  pure  by  distilling 
glycerine  with  sulphuric,  or  phosphoric  acid.  The 
formula  of  acrolein  is  C3H4O2;  it  is  also  produced  in 
the  dry  distillation  of  all  fatty  bodies  which  contain 
glycerine.  If  glycerine  be  made  to  fall  drop  by  drop 
upon  platinum  black,  it  unites,  like  alcohol  and 
glycol,  with  O-2  and  glyceric  acid  is  formed. 

C3H803  +  0,=C3II604  +  H,0. 
The  oxidation  of  the  glycerine  does  not  stop  here; 


66  OKGANIC     CHEMISTRY. 

there  is  subsequently  formed,  acetic,  formic,  and  car- 
bonic, but  chiefly  oxalic  acid.  The  action  of  acids  on 
glycerine  demonstrates  two  facts;  first,  that  glycerine 
is  an  alcohol;  second,  that  it  is  a  triatomic  alcohol. 
On  treating  glycerine  with  hydrochloric  acid  the  first 
reaction  is  similar  to  that  between  alcohol  and  this 
acid, 

HC1+C3H803=C3TT7C102+H20. 

Monochlo:hydric  ether, 

or 
Monochlorhydriu. 

The  continued  action  of  phosphoious  perchloride 
upon  glycerine,  or  the  dichlorhydrate  of  glycerine, 
effects  the  elimination  of  additional  molecules  of  water 
and  the  formation  of  trichlorhydrin. 

3HC1+C3H803=C3H5C13  +  3(H20) 

Trichlorhydrin. 

Berthelot  has  studied  the  acetines,  butyrines  (tri- 
butyrine  exists  in  butter),  yalerines,  and  many  other 
ethers  of  glycerine.  If  glycerine  is  mixed  with  cold 
nitric  acid,  and  sulphuric  acid  added  drop  by  drop,  an 
oily  substance  separates  out  which  is  trinitroglycerine 
C3H5(NO2)3O3.  This  body  detonates  with  great  vio- 
lence. It  acts  very  energetically  on  the  system.  A 
few  drops  placed  on  the  tongue  produce  violent  me- 
grim. Glycerine  forms  compounds  with  lime  anal- 
ogous to  those  formed  by  sugar,  according  to  P.  Car- 
les, '  1-174-87). 


ALCOHOLS.  67 

USES. — The   uses   of  glycerine    in  the    arts,   and 

especially  in  pharmacy,  are  numerous  and  important, 
many  of  which  are  based  upon  the  solvent  power  of 
this  compound.  Henry  Wurtz  (31-195-58)  has  made 
valuable  suggestions  as  to  its  economical  applications. 

TABLE   SHOWING  THE   SOLUBILITY  OP    SOME    CHEMICALS   IX  GLYCERINE,   (FROM 

KLEVER.)  ONE   HUNDRED  PARTS  OF  GLYCERINE  DISSOLVE   THE  ANNEXED 

QUANTITIES  OF   THE  FOLLOWING  CHEMICALS: 

Arsenous  oxide,  20.00 

Arsenic  oxide,  20.00 

Acid,  benzoic,  10.00 

"      oxalic,  15.00 

"      taniiic,  50.00 

Alum,  40.00 

Ammonium  carbonate,  20.00 

chloride,  20.00 

Antimony  and  potassium  tartrate,  5.50 

Atropia,  3.00 

Atropia  sulphate,  33.00 

Barium  chloride,  10.00 

Brucia,  2.25 

Cinchonia,  0.50 

"          sulphate,  6.70 

Copper  acetate,  10.00 

"     sulphate,  30.00 

Iron  and  potassium  tartrate,  8.00 

"    lactate,  16.00 

"    sulphate,  25.00 

Mercuric  chloride,  7.50 

Mercurous  chloride,  27.00 

Iodine,  1.90 

Morphia,  0.45 

Morphia  acetate,  20.00 

chlorhydrate,  20.00 

Phosphorus,  0.20 

Plumbic  acetate,  20.00 

Potassium  arsenate,  50.00 

"            chlorate,  3.50 

"            bromide,  25.00 

cyanide,  32.00 

iodide,  40.00 

Quinia,  0.50 

taunate,  0.25 


68  ORGANIC    CHEMISTRY. 

Sodium  arsenate,  50.00 

"      bicarbonate,  8.00 

"      borate,  60.00 

"      carbonate,  98.00 

"      chlorate,  20.00 

Sulphur,  0.10 

Strychnia,  0.25 

nitrate,  4.00 

"           sulphate,  22.50 

Urea,  50.00 

Veratria,  1.00 

Zinc  chloride,  50.00 

"     iodide,  40.00 

"     sulphate,  35.00 


ETHERS.  69 


ETHERS. 

SIMPLE    ETHERS. 

Ethers  are  products  formed  by  the  action  of  alcohols 
upon  acids. 

By  most  chemists  they  are  looked  upon  as  referable 

to  the  oxides  of  metals;  thus   2S3  1  O  and  ^2S5  i    O, 

CM3  )  C2JbL5  j 

may  be  regarded  as  the  oxides  respectively  of  methyl 
and  ethyl.  They  bear  the  same  relation  to  alcohols 
that  oxides  of  the  metals  do  to  the  hydrates. 

Potassium  hydrate  KOH. 

Ethyl  hydrate,  or  ethyl  alcohol  C2H3OH. 

Potassium  oxide  T^  i  O. 

&  } 


Ethyl  oxide  or  ethyl  ether  *     O. 


The  simple  ethers  are  mostly  liquid.  They  are  very 
slightly  soluble  in  water,  while  they  are  readily  soluble 
in  alcohol.  Exposed  to  the  action  of  alkaline  solu- 
tions they  regenerate  alcohol. 

C4H802+KHO  =  C2H60+KCoH  O2. 


70  ORGANIC     CHEMISTRY. 

ETHYL     ETHER. 

Synonyms  :    Vinic  ether,  sulphuric  ether,  common  ether. 
04H100  =  C*H' 

Density  .736. 
Density  of  vapor,  37. 
Specific  gravity  of  vapor,  2.586. 
Boiling  point,  35.5°. 

To  prepare  this  compound,  sulphuric  acid  is  heated 
with  alcohol  in  a  retort,  placed  in  a  sand-bath.  The 
ether  distills,  its  vapor  being  received  in  a  well  cooled 
condenser,  provided  with  a  long  tube  which  cond  ucts 
the  uncondensed  vapor  into  a  chimney. 

The  cork  adapted  to  the  tubulure  of  the  retort  is 
provided  with  two  openings;  in  one  is  fixed  a  ther- 
mometer, through  the  other  a  tube  passes  which  fur- 
nishes the  supply  of  alcohol.  All  the  connections 
should  close  perfectly.  When  the  apparatus  i  s  arranged 
in  this  manner,  pour  TOO  grams  of  85  percent,  or  90  per 
cent,  alcohol  into  the  retort,  and  add,  little  by  little,  100 
grams  sulphuric  acid  of  1.84  sp.  gr.,  then  heat.  When 
the  thermometer  attains  130°,  cause  the  alcohol  to 
flow  from  the  upper  vessel  at  a  rate  sufficient  to  keep 
the  temperature  between  130°  and  140°.  The  weight 
of  alcohol  capable  of  being  transformed  into  ether  is 
from  13  to  15  timas  the  weight  of  the  mixture  first  in 
troduced  into  the  retort.  The  distilled  liquid  is  mixed 


ETHERS.  71 

with  12  parts,  to  every  100  of  its  weight,  of  a  solution 
of  soda  having  a  specific  gravity  of  1.32,  and  agitated 
from  time  to  time,  during  -±8  hours. 

The  ether  is  decanted  by  means  of  a  glass  siphon, 
redistilled  and  four-fifths  of  the  liquid  collected.  The 
remainder  may  serve  for  a  future  operation. 

This  furnishes  ordinary  ether.  To  further  purify, 
wash  with  water,  decant  and  treat  for  two  days  with  equal 
parts  of  quick  lime  and  fused  calcium  chloride.  Wil- 
liamson has  clearly,  shown  that  etherification  takes 
place  in  two  stages  or  successive  reactions  as  follows  : 

C2H6  +  H2S04  =  II20  +  (CaH5)HS04. 

Ethylsulphuric  acid. 

(C2H5)HS04  +  C2HeO  =  C4H100  +  H2SO4. 


This  explains  how  a  small  quantity  of  sulphuric 
acid  etherizes  a  large  amount  of  alcohol,  since  sul- 
phuric acid  is  constantly  regenerated.  This  is  con- 
firmed by  the  following  experiment.  Iodide  of  ethyl 
is  made  to  react  upon  potassium  alcohol  ;  ether  is 
obtained  as  indicated  by  the  reaction; 

C2H5I  +  C2II5OK  =  C4H100  4-  KI. 

Ether  is  a  neutral,  volatile  liquid,  colorless,  having  a 
burning  taste  and  a  strong  agreeable  odor.  When 
agitated  with  water  it  rises  to  the  surface,  but  the 
water  dissolves  about  one  ninth  of  its  own  weight  of 
the  ether.  It  is  miscible  with  alcohol  in  all  propor- 


72  ORGANIC     CHEMISTRY. 

tions  and  with  wood  spirit.  Ether  is  frequently  adul- 
terated with  the  latter  substance.  Next  to  alcohol  it 
is  the  most  generally  employed  solvent  for  organic 
substances.  It  dissolves  resin,  oils  and  most  com- 
pounds rich  in  carbon  and  hydrogen. 

Bromine,  iodine,  chloride  of  gold  and  corrosive  sub- 
limate are  soluble  in  this  liquid.  It  dissolves  phos- 
phorus and  sulphur  in  small  quantity. 

"W.  Skey,  (8 — Aug.  3,  '77,)  has  shown  that  contrary  to 
the  usual  statement  in  standard  works,  ether  dissolves 
notable  quantities  of  the  alkalies. 

At  a  red  heat  it  is  decomposed  and  furnishes  carbon 
monoxide,  water,  marsh  gas  and  acetylene. 

It  is  exceedingly  inflammable,  and  burns  with  a 
bright  flame. 

Its  extreme  volatility,  the  density  of  its  vapor,  its 
insolubility  in  water  and  its  great  inflammability  render 
its  use  dangerous,  and  explosions  caused  by  it  are  of 
frequent  occurrence.  It  should  never  be  brought  near 
a  fire  or  light  in  open  vessels.  In  case  ether  inflames, 
it  is  best,  if  possible,  to  at  once  close  the  vessel  con- 
taining it,  and  thus  avoid  the  more  serious  conse- 
quences ensuing  from  an  explosion.  Exposed  to  the 
air  it  experiences  a  slow  combustion  as  in  the  case  of 
alcohol,  and  the  same  compounds  are  the  result. 

Chlorine  acts  violently  upon  it;  in  moderating  the 
action,  the  whole  or  a  part  of  the  hydrogen  may  be 
replaced  atom  for  atom  by  chlorine. 

USES. — It  is  used  in  pharmacy  in  preparing  etherial 


ETHERS.  73 

tinctures,  and  as  an  antispasinodic  and  stimulant  in 
the  well-known  Hoffmann's  anodyne.  Its  most  impor- 
tant use  in  medicine  is  as  an  anesthetic,  than  which 
none  is  safer  or  more  reliable  in  efficient  hands.  It 
is  extensively  employed  in  the  laboratory  and  in 
photography. 

COMPOUND    ETHERS 

are  bodies  built  up  on  the  type  of  water,  having  one 
half  the  hydrogen  replaced  by  a  hydrocarbide  and  the 
other  half  by  a  compound  radicle  containing  oxygen, 
or,  in  other  words,  by  the  radicle  of  an  acid. 

ACETIC  ETHEK,  (r?H  r\\   C  O- 
)  ) 


To  prepare  this  ether  8  parts  of  very  concentrated 
alcohol  are  distilled  with  7  parts  of  sulphuric  acid  and 
10  parts  of  anhydrous  sodium  acetate,  which  may  be 
replaced  by  20  parts  of  dry  lead  acetate.  The  distil- 
late is  agitated  with  a  solution  of  calcium  chloride 
containing  milk  of  lime,  decanted,  dried  over  calcium 
chloride  and  finally  distilled. 

Seven  parts  of  water  dissolve  one  part  of  this  body. 
Alcohol,  and  ether  dissolve  it  in  all  proportions.  It 
is  a  solvent  for  many  organic  bodies.  It  is  easily  de- 
composed on  contact  with  water.  Potassa  also  effects 
this  decomposition  very  readily.  A  prolonged  action  of 
ammonia  transforms  it  into  acetamide  and  alcohol. 


74  ORGANIC    CHEMISTRY. 

OXALIC    ETHEKS. 

Oxalic  acid,  being  a  bibasic  acid,  furnishes  with 
alcohol  two  combinations,  one  being  acid  and  capable 
of  combining  with  bases  ;  the  other  is  neutral,  C6H10O4. 

Only  the  latter  is  of  interest.  It  may  be  prepared 
by  introducing  four  parts  of  90  per  cent,  alcohol  and 
four  parts  of  oxalic  acid  into  a  retort,  adding  to  this 
mixture  three  to  six  parts  of  sulphuric  acid  and  then 
rapidly  distilling  ;  the  product  is  washed  several  times, 
dried,  then  redistilled,  collecting  only  the  liquid  which 
passes  over  at  184°.  This  ether  is  aromatic,  oily,  and 
gradually  decomposes  in  water. 

Potassium  changes  it  into  carbonic  ether. 

If  oxalic  ether  is  agitated  with  ammonia,  a  white 
powder,  oxamide,  and  ethyl  alcohol  are  produced. 


(C2H5)2 


2  1 

'    i 

} 


II,  = 


Oxamide  may  be  considered  as  derived  from  two 
molecules  of  ammonia,  and  belongs  to  a  class  of  bodies 
called  diamides. 

It  is  a  white  substance,  insoluble  in  cold  water  and 
alcohol.  Heated  with  mercuric  oxide  it  is  transformed 
into  carbon  dioxide  and  urea.  (Williamson.) 


ETHERS.  75 

Oxalic  ether  treated  with  ammonia  in  solution  in 
alcohol  furnishes  oxamic  ether. 

In  this  connection  the  compound  of  the  organic 
radicles  with  the  haloid  elements  are  usually  studied: 
they  are  not  unfrequently  denominated  ethers  of  the 
hydracids.  Their  type  is  a  molecule  of 

TT    \ 

hydrogen,  H  j-  . 

CHLORIDE  OF  ETHYL  OK  CHLOKHYDKIC  ETHER. 


Cl  f  ' 

This  body  is  formed  in  small  quantity  when  ethy- 
lene  is  made  to  react  upon  hydrochloric  acid. 

To  prepare  it,  alcohol  contained  in  a  flask  sur- 
rounded by  cold  water,  is  saturated  with  hydrochloric 
acid  2as  and  the  mixture  then  distilled. 

o 


It  is  also  obtained  by  pouring  into  a  flask  contain- 
ing 2  parts  common  salt,  a  mixture  of  1  part  alcohol, 
and  1  part  sulphuric  acid  :  it  is  then  gently  heated 
and  the  ether  collected  as  previously  shown. 

It  is  a  liquid  of  an  agreeable  odor,  and  very  volatile, 
having  a  boiling  point  of  12°  and  a  vapor  density  of 
64°.  A  red  heat  decomposes  it  into  ethylene  and 
hydrochloric  acid  gas.  It  is  combustible  and  burns 
with  a  green,  smoky  flame  ;  water  dissolves  the  fif- 
tieth part  of  its  volume,  alcohol  dissolves  it  completely. 


76  ORGANIC    CHEMISTRY. 

With  chlorine  it  furnishes  a  complete  and  regular 
series  of  products  of  substitution  which  are  not  iden- 
tical, but  isomeric  with  the  chlorine  products  of 
ethene. 

Their  formulae  are: 

C2H4C12 

Cg-tlgC^ 

C2H,CJ4 
C2H  C15 
C2  C16. 

IODIDE   OF    ETHYL   OR    HYDKOIODIC    ETHER. 


C.H,I  = 


C2H5 1  ? 


is  obtained  on  causing  alcohol  to  react  upon  iodide  of 
phosphorus;  the  action  is  violent  with  white  phos- 
phorus, considerably  less  so  with  red  phosphorus. 

Six  hundred  grams  of  concentrated  alcohol  are  intro- 
duced into  a  retort  with  140  grains  of  amorphous 
phosphorus,  and  to  this  mixture  450  grams  of  iodine 
are  added.  The  distilling  is  carried  nearly  to  dryness. 
The  product,  condensed  in  the  receiver,  is  washed  with 
water  containing  a  little  potassa ;  afterwards  with  pure 
water.  It  is  then  dried  over  calcium  chloride  and 
again  distilled. 

Iodide  of  etlryl  is  a  colorless  liquid.  Its  density  is 
1.975.  It  becomes  colored  on  exposure  to  light,  being 
slightly  decomposed ;  it  is  again  rendered  colorless  on 
agitating  it  with  an  alkaline  solution,  which  absorbs  the 


ETHERS.  77 

acid  formed.  It  burns  with  a  green  flame,  leaving  a  resi- 
due of  iodine.  Ammonium  compounds  in  alcoholic,  or 
aqueous  solution,  furnish  ethylamine.  This  arnine  can 
be  attacked  in  its  turn  by  iodide  of  ethyl  and  yields 
diethylamine  and  oxide  of  tetrethylammonium.  The 
knowledge  of  these  reactions  and  their  application  to 
other  iodides  are  the  basis  of  a  general  mode  for  the 
preparation  of  organic  bases  originated  by  Hoffmann. 
Iodide  of  ethyl,  unlike  the  chloride,  is  readily  decom- 
posed by  solutions  of  silver  nitrate,  giving  a  precipi- 
tate of  silver  iodide. 


=  (C.JI5) 

CYANIDE  OF  ETHYL  OR  CYANHYDKIC  ETHER. 


This  ether  is  obtained  on  distilling  in  an  oil-bath 
1  part  of  potassium  cyanide,  with  1-5  part  of  an  alkaline 
sulpho-vinate.  To  the  product,  redistilled  in  a  bath  of 
salt-water,  nitric  acid  is  slowly  added  in  excess  ;  it  is 
then  subjected  to  another  distillation.  Finally,  it  is 
dried  over  calcium  chloride,  and  that  which  passes  over 
from  195°  to  200°  is  collected  on  redistillation. 

Cyanide  of  ethyl  is  a  colorless  liquid  of  an  alliaceous 
odor,  boiling  at  97.°. 

Cyanide  of  ethyl  is  decomposed  by  potassium  hy- 
drate; ammonia  is  produced,  and  the  acid  obtained 
corresponds  with  a  higher  homologous  alcohol. 


78  ORGANIC     CHEMISTRY. 

3H602. 

Propionic  acid. 

M.  Meyer  observed  some  years  ago,  that  if  cyanide 
of  silver  is  treated  with  iodide  of  ethyl,  a  liquid  is 
formed,  boiling  at  82°,  of  an  odor  which  is  not  that  ot 
ordinary  cyanhydric  ether.  Gautier  has  shown  that  this 
is  an  isomeric  body,  and  that  there  are  two  isomeric 
series  of  cyanhydric  ethers.  Hoifmann  has  given  a  dis- 
tinctive character  to  these  bodies:  under  the  influence 
of  the  alkalies  they  produce  a  fixed  substance,  but 
this  is  formic  acid  and  not  ammonia,  and  a  volatile 
substance  which  is  a  compound  ammonia. 

H   ) 
CN(C2H5) + 2H2O=  CHA  +  CJ15  V  N. 

TT       \ 

' — —  J±       ) 

Formic  acid.       Ethylamine. 

ORGANO-METALLIC  COMPOUNDS. 

Iodide  of  ethyl  attacks  the  metals  and  furnishes  a 
class  of  bodies  called  organo-metallio  radicles.  None 
of  these  bodies  are  found  in  nature.  They  are  formed 
from  the  iodohydric  ethers  by  the  substitution  of  a 
metal  for  the  iodine; 

Zn  +  2(OaH5I)  =  (C2H5)2Zn  +  ZnI2, 
2Sn  -f-  2(C2H5I)  =  (C2H5)2Sn  +  SnI2. 

Practically  these  metallic  radicles  are  obtained  by 
various  reactions: 


ORGANO-METALLIC  COMPOUNDS.  79 

1.  By  the  action  of  the  metal  upon  the  iodide,  for 
example; 

2C2H5I  +  Zn=(C2H5)2Zn  4-  Znla. 

In  certain  cases,  with  tin  for  instance,  the  reaction  is 
not  as  distinct,  and  there  is  formed  in  addition  to  stan- 
nethyl  iodide,  stannethyl  iodides  variously  condensed. 

2d.  The  metal  is  treated  with  another  radicle;  thus 
sodium-ethyl  is  prepared  by  the  action  of  sodium 
upon  zinc  ethyl, 


(C2H5)2Zn  +  Na2=Zn  +  2C2H5Na. 

3d.  On  decomposing  a  metalloid  compound  radicle 
with  a  metallic  chloride, 

3ZnCl2  +  (C2H5)3P=3(C2H5)Zn  +  2PC13. 

4th.  Stannethyl  is  obtained  by  plunging  a  plate 
of  zinc  into  a  soluble  salt  of  this  radicle:  the  radicle 
is  precipitated  in  the  form  of  an  oily  liquid. 

Cacodyl,  As  (CH3)2  was  the  first  discovered  of  this  class 
of  bodies.  It  was  obtained  by  Bunsen  on  distilling 
arsenous  acid  with  potassium  nitrate.  The  organic 
radicles  combine  with  metalloids  with  more  or  less 
energy  ;  zinc  -ethyl  and  cacodyl  take  fire  in  the  air  ; 
they  also  decompose  water.  The  products  of  oxida- 
tion vary  with  the  nature  of  the  compounds  employed; 
zinc-ethyl  furnishes  the  body,  CJI3ZnO,  zinc-ethyl- 
ate,  which,  in  contact  with  water,  produces  alcohol  and 
oxide  of  zinc.  The  metals  which  are  less  readily  oxy- 


80  ORGANIC     CHEMISTRY. 

dized,  such  as  tin,  lead  and  mercury,  give  oxides 
which  play  the  parts  of  bases,  and  these  latter  com- 
port themselves  like  the  oxides  of  the  metals  they  con- 
tain. Finally,  the  radicles  formed  by  the  elements, 
phosphorus,  arsenic,  and  antimony,  give,  with  oxy- 
gen, -compounds  which  generally  have  the  character  of 
acids. 

Some  of  the  organic  derivatives  containing  phos- 
phorus are  very  complex.  For  instance,  J.  Auanoff 
(60-' 75-493)  has  obtained  a  body  he  denominates, 
methyldiethylphosphoniumphenyloxidehydrate! 

To  prepare  zinc-ethyl,  we  introduce  into  a  flask 
connected  with  a  condenser  inclined  in  such  a  manner 
that  the  vapors  find  their  way  back  into  the  flask,  100 
grams  iodide  of  ethyl,  75  grams  of  zinc,  and  6  to  7 
grams  of  an  alloy  of  zinc  and  sodium,  and  heat  in 
the  water  bath  until  the  zinc  is  dissolved ;  then  the 
condenser  is  inclined  as  usual,  and  the  distilling  is 
effected  over  a  direct  fire,  collecting  the  liquid  pro- 
duct in  a  flask  Billed  with  dry  carbon  dioxide. 
Finally  it  is  again  distilled  in  this  gas,  and  that  col- 
lected'which  passes  over  from  116°  to  120°.  All  the 
vessels  and  all  the  substances  should  be  absolutely 
dry,  and  it  should  always  be  collected  and  distilled  in 
vacua,  or  in  carbon  dioxide.  It  is  a  colorless  liquid, 
whose  density  is  1.182,  boiling  at  118°,  inflammable 
on  exposure  to  the  air. 

With  sodium  this  body  furnishes  sodium-ethyl,  and 
with  chloride  of  phosphorus  or  arsenic,  it  furnishes 
triethyl  phosphine,  P(C2H5)3,  and  trietbyl  arsine, 
As  (C2H5)3. 


ETHERS.  81 

Mercury-methyl,  treated  with  iodine,  furnishes  a 
hydrocarbide  which  has  the  formula  ol  methyl,  CH3. 

'  Professors  Crafts  and  Friedel  (72-[4]19-334)  have 
prepared  a  large  number  of  compounds  of  silicon  with 
compound  radicles,  from  which  they  have  deduced 
valuable  theoretical  considerations. 

MISCELLANEOUS  ETHEES. 

Formic,  butyric,  valerianic  ether,  and  other  ethers 
of  the  fatty  series  are  prepared  in  the  same  manner  as 
acetic  ether,  and  have  the  general  properties  of  this 
ether.  The  odor  of  these  ethers  is  agreeable.  Bu- 
tyric ether  has  the  odor  of  pine-apple,  and  valerianic 
ether  that  of  pears  ;  cenanthylic  ether  has  ths  aroma 
of  wine,  etc.  They  are  used  in  the  manufacture  of 
syrups,  flavoring  extracts,  and  for  imparting  an  odor 
to  liquors. 

If  the  difference  between  the  points  of  ebullition  of 
these  ethers  is  examined  it  will  be  seen  that  the 
addition  of  the  elements  CIT2  causes  an  elevation  of 
about  20°  in  the  point  of  ebullition.  Kopp  has 
shown  that  this  fact  is  a  general  one  and  applies 
to  the  alcohols,  and  acids  of  the  same  series,  and  to 
the  homologous  bodies  in  general. 

Point  of  ebullition.  Difference. 
Formic    ether,      -        -       55°  1q0 

Acetic         "      -  74:°  o^o 

Propionic   "     -         -  95°  |t0 

Butyric       «  -       119°  fjo 

Yalerianic"     -         -          133° 


82  ORGANIC    CHEMISTRY. 

The  boiling  point  of  one  of  these  bodies  may  accord- 
ingly be  predicted,  if  that  of  one  of  its  homologous 
substances  is  known.  There  is  a  certain  close  relation 
between  the  point  of  ebullition  of  an  ether  and  that 
of  the  acid  whose  radicle  it  contains: 

Point  of  ebullition.     Difference. 

Formic  acid,  105°  ) 

"       ether,  -        55°  f                      50° 

Acetic  acid  -    118°) 

u      ether,  74°  f                     44° 

Propionic  acid,  -      140°  / 

"      ether,  -                      95°  j                      45° 

Butyric  acid,  -         -         163° 


ether,     -  -    119°  f  44° 

The  solubility  in  water  of  the  ether  formed  by 
homologous  acids  varies  with  the  molecular  weight ; 
thus  formic  ether  is  quite  soluble,  acetic  ether  is  less 
soluble,  butyric  ether  is  but  slightly  so,  and  valerianic 
ether,  which  follows  it,  is  nearly  insoluble. 

MERCAPTANS    AND    THEIR    ETHERS. 

On  substituting  sulphur,  selenium,  or  tellurium  for 
oxygen  in  the  alcohols  of  different  atomicity,  sulphur, 
selenium,  or  tellurium  alcohols  are  obtained,  which 
are  designated  as  mercaptans,  selenium  mercaptans, 
and  tellurium  mercaptans. 

Ethers  proper  correspond  to  these  as  to  ordinary  al- 
cohols. These  ethers  are  derived  either  by  the  substi- 


ETHERS.  83 

tution  of  an  alcohol  radicle  for  the  typical  hydrogen, 
as  happens  with  monatomic  mercaptans,  or  by  the 
elimination  of  H2S,  as  is  the  case  with  biatomic  mer- 
captans. 

One  only  of  each  of  these  two  classes  will  be  alluded 
to  here. 

Ethyl  sulphide,  or  hydrosulphu-  )  n  TT  c     C2H5  )  Q 
ric  ether,  f  °4Ml°b  =C2H5  f  b' 

Ethyl  mercaptan,  C4H6S=°2g5  j-  S. 

To  prepare  the  sulphide  a  current  of  ethyl  chloride, 
is  passed  into  an  alcoholic  solution  of  potassium 
sulphide. 

The  mercaptan  is  prepared  by  the  action  of  potass- 
ium hydro-sulphide  or  ethyl  sulphide. 

In  either  case  potassium  chloride  is  formed. 

K2S  +C2H4C1==C4H10S  +  2KC1 
KHS  +  C2H5C1=C2H6  S  +  KC1. 

These  bodies  are  afterwards  separated  by  distillation- 
Like  all  the  sulphur  derivatives  of  alcohol,  they  have  a 
nauseous  odor.  The  sulphide  boils  at  91°  the  mer- 
captan at  36°. 

MIXED    ETHERS 

containing  two  different  radicles,  are  obtained  by  act- 


84  ORGANIC    CHEMISTRY.. 

ing,  for  instance,  with  ethyl  iodide  upon  potassium 
me  thy  late,  thus  : 


ethyl  iodide,    potassium     potassium   methyl-ethyl 
methylate.         iodide.  ether. 

CTT   ) 
or  by  acting  on  hydric  methyl  sulphate  j-  SO4 

with  ethyl  alcohol.  The  following  is  a  list  of  some  of 
the  more  important  mixed  ethers  of  the  monatomic 
series 


TABLE   OF   MIXED  ETHEKS.  BOILING   POINT. 

Methyl-ethyl  ether  C8H8O=  Q  |[3  I  O         +  11° 


Methyl-amyl  ether  C6H14O  =      j^    °  92° 

Ethyl-butyl  ether  C6H14O  =  ^2^5  1  O          80° 
Ethyl-amyl  ether   C7H16O  =  ^2^5  i  O         112° 


Ethyl-hexyl  ether  C8H18O  =        *      O         132° 


ALDEHYDS.  85 


ALDEHYDS. 

The  following  are  the  principal  aldehyds,  arranged 
in  series: 

CnH2nO. 

Formic  aldehyd      -                 -  C  H2  O 

Ethylic  aldehyd  Oa  H4  O 

Propylic  aldehyd   -                 -  C3H6O 

Butylic  aldehyd   -  C4H80 

Valeric  aldehyd  C5  H10O 

(Enanthylic  aldehyd      -        -  C7H14O 

Caprylic  aldehyd    -                 -  C8H16O 

Caproic  aldehyd  CjoH-^O 

Eutic  aldehyd  CnH^O 

Ethalic  aldehyd  C^H^O 

CnH2n.20. 

Ally  lie  aldehyd  (acroleiri)  -  C3  H4O 

CnH2n40. 
Campholic  aldehyd  (camphor)  C10H16O 


86  ORGANIC    CHEMISTRr. 


Benzole  aldehyd  (oil  of  bitter  almonds)  C7  H6  0 
Tolnic  aldehyd  C8  H8  O 

Cuminic  aldehjd  -  C10H12O 

Sycocerylic  aldehyd  C18H28O 

CnH2n..10O. 

Cinnamic  aldehyd  (oil  of  cinnamon]     -     C6H8O. 

Aldehyds  may  be  regarded  as  bodies  built  upon  the 
type  of  one  or  more  molecules  of  hydrogen,  in  which 
one  half  the  hydrogen  atoms  are  replaced  by  one  or 
more  molecules  of  an  oxidized  carbohydride. 

The  formation  of  aldehyd, 
may  be  illustrated  by  the  following  equation: 

C2H60-H2  —  C2H4O 


Ethyl  alcohol.  Ethyl  aldehyd. 

Aldehyds  are  obtained  by  the  oxydation  of  alcohols, 
but  they  are  only  the  first  products  of  oxydation.  They 
are  capable  of  combining  with  an  additional  molecule  of 
oxygen,  forming  acids;  hence  the  aldehyds  are  inter- 
mediate between  alcohols  and  acids. 

ORDINARY    ALDEHYD. 


H 

This  substance  is  formed  by  the  slow  oxydation  of 
alcohol. 


ALDEHYDS.  87 

•\ 

Alcohol  is  treated  with  a  mixture  of  manganese 
binoxide,  or  of  potassium  bichromate,  and  sulphuric 
acid,  and  distilled,  care  being  taken  to  keep  the  re- 
ceiver well  cooled.  Besides  aldehyd,  acetyl,  acetic 
ether,  acetic  acid  and  water  are  formed.  The  product 
is  again  distilled,  care  being  taken  to  collect  only  that 
portion  which  passes  over  above  60°.  This  liquid  is 
mixed  with  ether,  and,  when  cool,  a  stream  of  dry 
ammonia  gas  is  caused  to  pass  through  the  solution. 
Crystals  of  ammonium  aldehyd  are  formed, 
C2H3(NH4)O,  which  are  decomposed  by  dilute  sul- 
phuric acid.  The  mixture  is  then  distilled. 

Aldehyd  is  a  colorless,  very  volatile  liquid.  It  is 
soluble  in  water,  alcohol  and  ether,  and  possesses  a 
strong,  somewhat  stifling  odor. 

The  salient  property  of  aldehyd  is  its  avidity  for 
oxygen.  If  a  few  drops  are  poured  into  water  the 
latter  becomes  acid;  it  is  therefore  a  valuable  reduc- 
ing agent. 

If  aldehyd,  or  ammonium  aldehyd,     VVj   f    is 

poured  into  an  ammoniacal  solution  of  silver  nitrate, 
on  slightly  elevating  the  temperature,  metallic  silver  is 
deposited.  This  silver  adheres  to  the  sides  of  the  tube, 
and  covers  it  with  a  mirror-like  coating.  This  prop- 
erty is  the  basis  of  a  process  of  silvering  glass  globes 
and  other  hollow  articles  of  glass. 

Aldehyd  is  attacked  by  chlorine  and  bromine,  and 
furnishes,  by  substitution,  various  products,  of  which 

CHLORAL   C2IIC13O,  is  the  most  important.     Hy. 


88  ORGANIC    CHEMISTRY. 

drate  of  chloral,  or  C2HC13O  +  II2O,  hasbeen  prepared 
now  for  several  years  in  very  large  quantities,  for 
medicinal  purposes.  Its  name  is  derived  from  chlor- 
ine  alcohol. 

Absolute  alcohol  is  saturated,  first  cold,  then  hot, 
with  dry  chlorine.  The  liquid  obtained  is  mixed  with 
its  volume  of  concentrated  sulphuric  acid.  The 
supernatant  liquid  is  decanted,  and  distilled  in  an 
earthern  retort,  with  one-fourth  its  weight  of  sulphuric 
acid.  The  anhydrous  chloral  obtained  is  re-distilled 
twice  with  calcium  carbonate  and  1  to  8  per  cent,  of 
water.  The  hydrate  is  then  obtained  in  handsome 
crystals,  C-^HClsO  +  H.^O,  soluble  in  water.  It  has 
been  known  for  some  time  that  this  body  is  decom- 
posed in  presence  of  alkalies  or  alkaline  carbonates, 
into  chloroform  and  formic  acid, 


Potassium    Chloroform. 
formiate. 

The  question  appeared  pertinent  whether  a  similar 
transformation  would  be  affected  in  the  human  body, 
under  the  action  of  the  alkaline  fluids  there  present, 
notably  those  of  the  blood,  and  thus  develop  chloro- 
form. 

Liebreich  was  the  first  to  administer  chloral,  and  he 
at  once  obtained  the  anesthetic  effects  of  chloroform. 
His  experiments  were  repeated  in  different  countries, 
and  hydrate  of  chloral  soon  came  into  general  use  as 
a  hyponotic. 


ALDEHYDS  89 

Chloral  hydrate  for  medical  use  must  be  crystalline 
and  possess  the  following  properties:  it  should  be  col- 
orless, transparent,  and  have  an  aromatic  odor,  a  caus- 
tic taste,  readily  soluble  in  water  without  furnishing 
drops  of  oil,  also  soluble  in  alcohol,  ether,  naphtha, 
benzol,  and  carbon  bisulphide;  it  should  fuse  at  56°  to 
58°,  solidify  at  about  15°,  boil  and  volatilize  completely 
at  95°.  With  caustic  potassait  should  furnish  chloro- 
form, and  with  sulphuric  acid,  chloral,  without  becom- 
ing brown.  Its  aqueous  solution  should  be  neutral 
and  not  produce  any  turbidity  with  silver  nitrate  and 
nitric  acid.  Exposed  to  the  air  it  shor.ld  not  become 
moist.  According  to  recent  investigations  by  Liebreich, 
(60-69-673)  chloral  produces  the  opposite  physiolog- 
ical effects  of  strychnine,  hence,  these  bodies  may 
be  used  as  antidotes  one  for  the  other 

The  remaining  aldehyds  are  not  sufficiently  im- 
portant for  a  work  of  this  scope.  Camphor  has  al- 
ready been  considered  in  connection  with  turpentine. 


90  ORGANIC     CHEMISTRY. 


OEGAOTC  ACIDS. 

ACIDS  CONTAINING   TWO   ATOMS   OF   OXYGEN. 
FATTY    ACID    SERIES. 


Formic        acid,  -  C  H2  O2 

Acetic  "  C2  H4  O2 

Propionic  "  C3  H6  O2 

Butyric  "  C4H8(X 

Valeric  "  C5 II10O2 

Caproic  "  -  C6H12O2 

(Enanthylic  "  C7H14O2 

Caprylic  i(  C8  H16O2 

Pelargonic  "  -                         C9H18O2 

Capric  CJOIL0O2 

Laurie  "  -                        C12H24O2 

Coccinic  C13H26O2 

Myristic  "  -                        C14H28O2 

Palmitic  "  C16II32O2 

Margaric  C17H34O2 

Stearic  C18H36O2 

Arachidic  -  "  .             C2oH40O2 

Cerotic  O27H54O2 

Melissic  " 


ORGANIC    ACIDS.  91 


CaH2n...A. 

Acrylic      acid     - 

C  H402 

Crotonie        " 

C4H.Oa 

Angelic          "     - 

C5H802 

Pyroterebic   " 

C6H1002 

Campholic     "     - 

C10H1802 

Moringic       *' 

-  CtfPIajOa 

Physetoleic  " 

C16H.3oO2 

Oleic              « 

C18H34O2 

Doeglic         '' 

C^IlseO, 

Erucic           " 

C\    TT    C\ 
\JnSjLjB\J*, 

Sorbic    acid  C6  H8  O2 

Camphic  "  C10H16O2 

AROMATIC   ACID    SERIES. 


Benzoic  acid  C7  H6  O2 

Toluic       "  C8  H8  O2 

Xylic        "  C9H1002 

Cumic       6t  -     C10H12O2 

Alpha-cymic  acid  ( 


Cinnamic  acid  C9II8O2 

Pinic  "      - 


92  ORGANIC     CHEMISTRY. 

ACIDS   CONTAINING   THREE   ATOMS  OF  OXYGEN, 
CnH2nO3. 

Carbonic  acid  C  H2O3 

Glycolic  "      -  -    C2H4O8 

lactic  "  C3H6O, 

Oxybntyiic  "  C4H8O3 

Oxyvaleric  "  C5  H10O8 

Leticic  "    -  -      C6H12O8 

(Enanthic  "  CuBaA- 


Pyrnvic        acid  C3  H4  O 

Scammonic     "  C13H28^3 

Kicinoleic       "  CigH^Os 


Guaiacic       acid  C6  H8  O3 

Lichenstearic  "     -  -     C9  H14O3. 


Pyromeconic  acid  -                 C5  H4  O3. 
CnH2n_8O3. 

Salicylic     acid    -  -       C7H6O3 

Anisic  -     C8  Hs  O3 

Phloretic      "  C9H:0O> 

Oxycuminic  "  -     C10H12O^ 

Thymotic     u    -  CnH^Os. 


OKGANIC    ACIDS.  93 


Coumaric  acid      -  C9  H8  O3. 

ACIDS   CONTAINING   FOUR   ATOMS   OF   OXYGEN. 

CnH2n04. 
Gljceric  acid  C3H<jO4. 


Oxalic  acid  C2H2O4 

Malonic  "  C8H4O4 

Snccinic  "  C4H6O4 

Pyrotartaric  "  C5H8O4 

Adipic  "  CG  H;0O4 

Pimelic  "  C7  H13O4 

Suberic  "  C8II14O4 

Anchoic  «  C9H1604 

Sebic  "  C10H18O4 

Eoccellic  «  CHO. 


Fumaric  acid                C4  H4  O4 

Citraconic  u                   C5  H6  O4 

Terebic  "                   C7  H10O4 

Camphoric  " 

Lithofellic  " 


94  ORGANIC    CHEMISTRY. 


Mellitic  acid  C4H2O4 

Terechrysic       "  C6H6O4. 


Yeratric  acid  C9H10O4. 

CnH2n_10O.  * 

Phtalic                  acid  C8  H6  O4 

Insolinic                   u  C9II8O4 

Choloidic                  "  OHO 


Oxynaphthalic  acid  C10TI6  O4 

Pipeiic  "  C12H10O4. 

ACIDS    CONTAINING     5,     6,     7     AND     8     ATOMS   OF   OXYGEN. 


Tartronic  acid  C3H4O5 

Malic  «  C4H605. 


Mesoxalic  acid  C3H2O5. 


ORGANIC    ACIDS.  95 

Cholesteric  acid  C8H10O5. 


Croconic                 acid 
Comenic                     " 
Gallic                         " 
Cliolalic                      " 

C5H205 
C6H405 
C,H605 

Tartar  ic   acid 
Quinic        " 

04H,0, 

C7H12O6. 

Carballylic  acid 

C6H806. 

Aconitic  acid 

C6HA- 

Chelidonic  acid  C7H4  O6 

CnH2n_10O7. 
Meconic  acid  C7H4O7 

Citric  C6H«  O7 

Mucic  C6H10O8. 

Org  anic  acids  are  bodies  built  upon  the  type  of  one 
or  more  molecules  of  water,  having  one  half  the  hy- 
drogen replaced  by  an  organic  compound  radicle  con- 


96  ORGANIC     CHEMISTRY. 

taining  oxygen.  Tliere  are  some  acids  whose  compo- 
sition is  not  definitely  fixed.  "We  shall  first  examine 
the  monatomic  acids,  and  study  the  other  series  in  the 
order  of  their  atomicity. 

The  organic  acids  possess  the  general  properties  of 
the  mineral  acids.  Many  among  them,  like  acetic  acid, 
have  a  very  decided  action  upon  litmus.  Generally. 
they  are  solid  and  crystallizable;  however,  formic,  pro- 
pionic,  butyric  acids,  etc.,  are  liquid.  Acids  whose 
molecules  are  comparatively  simple,  are  ordinarily  sol- 
uble in  water  —  the  others  are  little,  or  not  at  all,  soluble 
in  this  solvent.  The  monobasic  acids  are  volatile,  at 
least  where  their  molecules  are  not  very  complex.  The 
polybasic  acids  are  decomposed  by  heat.  Their  salts 
are  ordinarily  crystallizable. 

METHODS   OF   PREPARATION. 

I.  The  acids  of  the  so-called  fatty  series  are  ob- 
tained by  the  oxidation  of  the  corresponding  alcohol, 
or  aldehyd,  which  latter  is  the  first  product  of  oxida- 
tion of  the  respective  alcohol. 


Acetic  aldehyd. 

C2H40-f02=C2HA. 


Acetic  acid. 


II.  These  acids  are  also  produced  by  the  action  of 
alkalies  upon  the  cyanide  of  the  radicle  appertaining 
to  the  homologous  inferior  alcohol. 


ORGANIC    ACIDS.  97 

(CH3)C]ST  +  KHO  +  H2O=NH3  +  KC2H8O8. 

Methyl  cyanide.  Potassium  acetate. 

III.  Acids  are  likewise  formed  by  the  union  of  the 
elements  of  carbon  monoxide  and  carbon  dioxide  with 
hydrogen  carbides  and  water.  The  remarkable  syn- 
thesis of  formic  acid  by  Berthelot  is,  according  to  this 
method : 

CO  +  H2O=CH2O2. 

Pelouze  has  shown  that  heat,  carefully  applied  to 
polyatomic  acids,  causes  them  to  part  with  a  certain 
number  of  molecules  of  water,  of  carbon  dioxide,  or  of 
both,  and  furnishes  acids  more  simple  and  of  a  lower 
equivalence,  which  he  designates  by  the  name  oipyro- 
acids. 

2C4H606=05H804 + 2H20  +  3COa . 

Tartaric  acid.  Pyro-tartaric  acid. 

Of  all  the  series  of  acids,  the  most  numerous  and  the 
most  important  are  those  of  the  so-called  fatty  series- 
We  shall  presently  indicate  the  methods  by  which  they 
are  obtained. 

Tneir  boiling  point  increases  from  15°  to  20°  with 
each  addition  of  CH2  to  their  molecule.  Certain  of 
their  salts,  those  of  calcium,  for  instance,  are  decom- 
posed by  heat,  furnishing  compounds  called  acetones. 


98  ORGANIC     CHEMISTRY. 

Ca(C2H802)2=CaC03  +  C8TI60. 

Calcium  acetate.  Ordinal  y  acetone. 

FORMIC    ACID. 

CH808=CH20 
H 

Red  ants  made  to  pass  over  moistened  blue  litmus 
paper  produce  red  stains.  The  acid  secreted  by 
these  insects  was  first  obtained  by  Gehlen,  and  has  re- 
ceived the  nr.me  of  formic  acid. 

I.  Berthelot    has  obtained  it    from    carbon    mon- 
oxide by  synthesis. 

II.  It  is  prepared  by   distilling  a  mixture  of  10 
parts  of  starch,  30  parts  of  sulphuric  acid,  20  parts  of 
water,  and  37  parts  of  manganese  binoxide  in  a  large 
retort  connected  with  a  condenser. 

The  mass  swells  considerably,  and  at  first  must  be 
heated  but  gently.  The  formic  acid  is  distilled  over 
and  saturated  with  lead  carbonate.  The  fbrmiate  of 
lead  is  caused  to  crystallize  in  boiling  water,  then 
placed  in  a  retort  and  decomposed  by  a  current  of  hy- 
drogen sulphide  and  thereupon  heated;  the  formic  acid 
is  then  distilled  off. 

III.  One  kilo  of  glycerine,  150  to  200  grams  of  water 
and  1  kilo,  of  oxalic  acid  are  introduced  into  a  retort 
and  heated  for  15  hours  at  a  temperature  of  about  100°. 
The  oxalic  acid  is  decomposed,  but  only  carbon  di- 
oxide is  disengaged.     Water  is'  added  from  time  to 


ACETIC    ACID.  99 

time,  and  the  mixture  then  distilled  until  8  litres  have 
passed  over.  The  glycerine  remains  unchanged  in  the 
retort,  and  can  again  he  used. 

Formic  acid  is  a  colorless  liquid,  of  a  very  acid  re- 
action, a  pungent  odor  and  crystallizing  at  about  0° 
and  boiling  at  101°. 

It  reduces  oxide  of  mercury,  furnishing  mercury,  as 
a  brown  powder,  also  carbon  dioxide  and  water.  Its 
salts  are  usually  soluble,  though  that  of  lead  is  very 
little  soluble  in  cold  water,  but  quite  soluble  in  boil- 
ing water. 

On  heating  with  sulphuric  acid,  carbon  monoxide 
and  water  are  formed. 

EXPERIMENT. — Introduce  into  a  test-tube  a  small 
quantity  of  formic  acid  or  a  formiate.  Add  sulphuric 
acid  and  heat;  a  regular  liberation  of  a  gas  takes  place, 
which  may  be  ignited,  producing  a  blue  flame. 


ACETIC  ACID. 
C2II402=C2H30 


30) 
II  f 


Sp.  Gr.  1.08.     Density  of  vapor  30. 

Glacial  acetic  acid  melts  at  17°;  boils  at  118°. 

This  is  the  acid  of  vinegar,  and  of  which  it  forms 
the  essential  part.  It  is  found  in  the  juices  of  many 
plants  and  in  certain  fluids  of  the  body.  It  is  formed 
by  synthesis  from  methyl,  sodium,  or  potassium  for- 


100  ORGANIC    CHEMISTRY. 

miate,  arid  by  the  oxidation  of  acetylene;  also  by  the 
action  of  nitric  acid  upon  fatty  substances,  and  by  the 
reaction  of  potassa  upon  tartaric,  malic  and  citric  acids. 
It  is  further  produced: 

I.  By  the  oxidation  of  alcohol  in  the  following  way: 
Wine  in  vats,  or  casks,  is  placed  in  a  cellar  main- 
tained at  a  temperature  of  about  30°;  every  sixth  or 
eighth  day  several  litres  of  vinegar  are  withdrawn  and 
replaced  by  an  equal  quantity  of  wine. 

Pasteur  has  established  that  the  oxydation  of  alco- 
hol is  produced  by  a  minute  plant,  the  Mycoderma 
aceti.  In  fact,  acetification  commences  only  when 
this  plant  has  been  formed  in  the  liquid.  If 
its  development  is  interrupted  the  oxydation  stops;  it 
renders  the  service  of  taking  oxygen  from  the  air  and 
transferring  it  to  the  alcohol. 

This  process  is  very  slow.  It  may  be  rendered  more 
rapid  by  pouring  dilute  alcohol  on  beach-wood  shav- 
ings placed  in  barrels.  The  air  penetrates  through 
openings  made  in  the  lower  portion.  The  alcohol, 
after  having  been  passed  over  the  shavings  four  times, 
will  be  found  sufficiently  acetified,  if  the  temperature  is 
maintained  at  about  25°. 

II.  DISTILLATION  OF  WOOD.     PYROLIGNEOUS    ACID. 
"Wood  is  distilled  in  retorts  ;  yielding  vapors  and  gases. 
The  former  are  condensed  by  causing  them  to  pass 
through  a  condenser  ;  the  gases  are  conducted  under 
the  retorts,  where  they  are  burned,  and  the  heat  util- 
ized in  the  distillation  of  the  wood. 

The  condensed  liquids  are  water,  acetic  acid,  wood 


ACETIC    ACID.  101 

spirit  and  tar ;  the  greater  portion  of  the  tar  is  me- 
chanically removed  and  the  remaining  liquid  distilled 
in  a  water  bath.  The  wood  spirit,  which  boils  at  63° 
passes  into  the  receiver.  The  water  and  acetic  acid 
remaining  in  the  retort  are  saturated  with  sodium 
carbonate,  the  product  is  evaporated  to  dryness  and 
heated  from  250°  to  350° ;  this  temperature,  while  not 
effecting  the  decomposition  of  the  sodium  acetate^ 
is  sufficient  to  carbonize  the  tarry  substance  remaining 
in  solution.  The  mass  is  thereupon  dissolved  in  water, 
filtered,  and  the  acetate  allowed  to  crystallize.  If  it  is 
desired  to  obtain  the  acetic  acid  uncombined,  the  solu- 
tion of  the  salt  is  distilled  with  a  slight  excess  of  sul- 
phuric acid. 

The  acetic  acid  which  distils  over  contains  a  large 
amount  of  water.  Normal,  or  anhydrous  acid  may  be 
obtained  from  it  by  saturating  half  of  the  liquid  with 
sodium  carbonate,  then  adding  the  remainder  to  this 
solution ;  acid  sodium  acetate  is  thereby  produced, 
which  is  evaporated  to  dryness  and  distilled  with  sul- 
phuric acid.  This  liquid,  cooled  with  ice,  gives  crystals 
of  normal  acetic  acid,  which  can  be  separated  on  de- 
canting the  liquid,  furnishing  the  so-called  glacial 
acetic  acid. 

Acetic  acid  is  liquid  above  17°;  below  that  it  crys- 
tallizes in  handsome  plates.  It  is  a  strong  acid,  has  a 
pronounced  odor,  and  is  very  caustic,  producing  blis- 
ters on  the  skin.  It  is  soluble  in  water,  alcohol  and 
ether  in  all  proportions.  It  dissolves  resin  and  cam- 
phor, also  fibrin  and  coagulated  albumen.  On  uniting 


102  ORGANIC    CHEMISTRY. 

with  water  it  contracts  in  volume.  A  red  heat  de- 
stroys it,  many  products  being  formed;  methane, 
acetylene,  acetone,  benzol,  naphthalin,  etc.,  also  car- 
bon, which  remains  in  the  retort. 

If  a  flask  containing  chlorine  gas  and  a  small  quan- 
tity of  acetic  acid,  is  exposed  to  the  sunlight,  trichlor- 

C  01  O  ) 

acetic  acid  is  formed,  '  3g  j-  O.  This  experi- 
ment of  Dumas  served  as  a  basis  for  the  theory  of 
substitution.  Le  Blanc  has  also  obtained  monochlor- 

acetic  acid  CoILCIO  /  ^      mi         1 1     • 

jj  j-  O.     These  chlorine  products  are 

reduced  to  the  state  of  acetic  acid  by  reducing  agents, 
such  as  sodium  amalgam  in  presence  of  water, 

(H2)3+C2HC1302-3HC1+C2H4O2. 

In  the  same  manner  as  acetic  acid,  heated  with  an 
excess  of  a  base,  furnishes  marsh  gas,  trichlor, 
acetic  acid  produces  trichlorinated  marsh  gas,  which 
is  chloroform, 

CaHA+BaO =BaCO8  +  CH4 
C2HCl302+BaO=BaC03  -f  CHC13. 

Perchloride  of  phosphorus,  in  the  hands  of  Gerhardt, 
has  become  the  means  of  an  important  discovery,  that 
of  acetic  anhydride  and  in  general  of  the  anhydrides 
of  the  monobasic-  acids.  If  dry  sodium  acetate  (3 
parts)  is  mixed  with  the  perchloride,  or  better,  with  oxy- 


VINEGAR.  103 

chloride  of  phosphorus,  (1  part),  and  then  distilled,  a 
chloride  is  obtained  called  acetyl  chloride, 

GJI3OCl=aH30  ( 
Cl 

acetyl  being  the  radicle  of  acetic  acid.  This  chloride, 
subjected  to  the  action  of  an  excess  of  sodium  acetate, 
is  decomposed  and  furnishes  acetic  anhydride, 

C,H30  )  0 
02iI30  C U> 

(also  called  acetate  of  acetyl)  or  acetic  oxide,  which 
boils  at  139°.  Water  destroys  it,  acetic  acid  being 
produced.  Chloride  of  acetyl  is  an  irritating  liquid, 
boiling  at  about  158°,  decomposable  by  water  into 
acetic  and  hydrochloric  acids. 

A  derivative  of  acetic  acid  of  considerable  theoretical 
importance  is  cyanacetic  acid  C3H3NO2=C2H3O  )  n 

CN  i  °' 

a  crystalline  body  forming  salts  with  the  metals,  which 
have  been  studied  by  T.  Menies.  On  acting  with  sul- 
phuric acid  and  zinc  on  cyanacetic  acid,  the  author 
[82-67-69]  obtained  formic  and  acetic  acids  and  am- 
monia. 

VINEGAR.  This  name  is  given  to  the  mixture  which 
is  obtained  by  the  acetification  of  wine,  whiskey,  infu- 
sion of  malt,  etc.  Good  acetic  vinegar  is  of  an  agree- 
able taste  and  aroma.  Wood  vinegar  has  a  very 
strong  disagreeable  taste  and  odor.  It  is  frequently 


104  ORGANIC    CHEMISTKY. 

adulterated  with  sulphuric  acid.  An  addition  of  1 
of  its  weight  of  this  acid  is,  however,  not  considered 
fraudulent,  as  its  presence  is  regarded  necessary  to 
prevent  moulding. 

A  ready  method  of  detecting  mineral  acids,  pro- 
posed by  M.  Witz  (77-75-268),  is  based  upon  the  use 
of  methyl-aniline,  which  undergoes  no  change  in  con- 
tact with  acetic  acid,  but  promptly  changes  to  a  green- 
ish-blue in  presence  of  the  least  trace  of  mineral  acid. 

Vinegar  and  concentrated  acetic  acid  are  employed 
in  medicine  as  stimulants. 

An  acetate,  or  acetic  acid,  can  be  recognized  by  heat- 
ing it  slightly  with  sulphuric  acid  and  alcohol  ;  a 
fragrant  odor,  characteristic  of  acetic  ether,  is  observed. 
Heated  with  sulphuric  acid  alone,  the  acetates  liberate  a 
vapor  which  has  the  odor  of  vinegar. 

The  following  reaction  permits  of  the  detection  of 
mere  traces  of  acetic  acid;  it  is  saturated  with  potas- 
sium carbonate  and  heated  with  arsenous  oxide  in  a 
test  tube;  fumes  and  a  nauseating  odor  are  given  off. 

The  author  finds  that  one  of  the  simplest  tests  for 
acetic  acid,  is  to  direct  a  fine,  yet  powerful  stream  of 
water  into  a  test-tube,  containing  .a  few  drops  of  the 
licjuid  to  be  tested.  The  very  fine,  white  eiferves- . 
cence  resulting  is  entirely  characteristic  of  this  acid, 
none  of  the  other  ordinary  acids  producing  the  same 
effect. 

Alcohol  should  not  be  present,  as  it  causes  a  similar 
effervesence.  If  the  acetic  acid  is  combined  it  should 
be  set  free  with  a  strong  mineral  acid.  By  this  test, 


ACETATES.  105 

perhaps  more  physical  than  chemical,  acetic  acid,  di- 
luted with  1000  parts  of  water,  can  be  readily  recog- 
nized, and  with  practice,  one  part  in  1500. 

ACETATES. 

Acetic  acid  is  monobasic;  there  are,  however,  alka- 
line biacetates  and  some  basic  acetates  of  copper  and 
lead. 

POTASSIUM    ACETATE. 


This  salt,  distilled  with  its  weigh  t  of  arsenous  oxide, 
furnishes  a  very  inflammable  liquid,  formerly  called  the 
"liquor  of  Cadet,"  and  in  which  Bunsen  has  found  a 
radicle  spontaneously  inflammable,  cacodyl,  C4H12As2. 

Potassium  acetate  forms,  as  well  as  sodium  acetate, 
an  acid  acetate  when  treated  with  acetic  acid.  It  is  a 
very  deliquescent  salt,  difficultly  crystallizable. 

AMMONIUM   ACETATE 

]STH4C2H802, 

Is  prepared  by  saturating  ammonium  carbon- 
ate with  acetic  acid.  Its  solution  constitutes  the 
spirit  of  Minder  erus ;  treated  with  phosphoric  oxide  it 
forms  cyanide  of  methyl.  There  is  also  an  acid  salt, 
OT34C2H3O,C2H4O.  In  compounds  of  this  character. 


106  ORGANIC     CHEMISTRY. 

acetic  acid  must  be  considered  as  acting  the  same  part 
as  the  water  of  crystallization  in  salts. 

SODIUM   ACETATE. 

]SaC2H3O2+3II20. 

This  is  used  in  preparing  marsh  gas  and  concentrated 
acetic  acid.  It  is  recommended  by  Tommase  (52-72- 
23),  as  a  solvent  for  plumbic  iodide,  of  which  two  grams 
are  readily  dissolved  in  0.5  c.  c.  of  a  strong  solution  of 
sodium  acetate. 

CALCIUM   ACETATE. 

Ca(C2H302)2. 

This  salt,  subjected  to  distillation,  furnishes  a  liquid 
containing  a  large  proportion  of  acetone  C3H6O- 

ALUMINUM   ACETATE. 

A1(C2H3O2)3. 

This  body  is  employed  at  present  by  dyers,  as  a  mor- 
dant. It  is  prepared  by  causing  aluminum  sulphate 
to  react  upon  lead  acetate.  Lead  sulphate,  which  is 
insoluble,  is  separated  on  filtering  the  liquid. 

FEEEIC    ACETATE. 

This  salt  (pyrolignite)  has  been,  and  is  still, 
somewhat  employed  for  the  preservation  of  wood. 


ACETATES  107 

COPPER    ACETATES. 

Normal  acetate  Cn(C2H3O2)9  is  called  verditer.  It 
iorms  beautiful  green  crystals  (crystals  of  Venus), 
which,  subjected  to  distillation,  furnish  acetic 
acid  mixed  with  acetone.  During  this  operation,  a 
white  sublimate  is  formed,  which  deposits  in  the  neck 
of  the  retort.  This  latter  is  cuprous  acetate,  and  is  car- 
ried over  into  the  receiver,  oxydizes,  and  changes  into 
cupric  acetate,  which  colors  the  distillate  blue.  There 
remains  in  the  retort,  after  this  decomposition,  very 
finely  divided  copper  which  takes  lire  when  slightly 
heated  in  the  air.  Solutions  of  this  acetate  reduce  the 
salts  of  the  oxide,  CuO,  and  serve  to  prepare  the  sub- 
oxide,  Cu2O. 

A  basic  acetate,  designated  by  the  name  of  verdigris, 
is  obtained  by  exposing  to  the  air  sheets  of  copper 
moistened  with  vinegar,  or  surrounded  by  the  marc  of 
grapes.  The  metal  becomes  covered  with  a  greenish 
incrustation  whose  formula  is, 

Cu(C2H3O2)2,CuO+6H2O. 

LEAD     ACETATE. 

The  normal  acetate  Pb(C2H3O2)2  is  prepared  by  treat- 
ing litharge  with  acetic  acid  in  slight  excess.  This  salt, 
known  by  the  name  of  sugar  of  lead,  crystallizes  in 
oblique  rhombic  prisms,  soluble  in  two  parts  of  water 
and  eight  parts  of  95  per  cent,  alcohol.  It  has  a  sweet 
taste,  and  is  very  poisonous.  It  is  employed  as  a  re- 


108  ORGANIC    CHEMISTRY. 

agent,  also  to  prepare  aluminum  acetate  and  lead  chro- 
mate. 

In  digesting  acetic  acid  with  an  excess  of  litharge,  it 
furnishes  a  hexabasic  acetate  of  lead.  If  ten  parts  of 
normal  acetate,  with  seven  parts  of  litharge  are  taken  and 
this  mixture  digested  with  30  parts  of  water,  there  are 
formed  minute  needles  of  a  tribasic  salt  Pb(C2H3O2)2, 
PbO2,H2O.  Finally  this  salt,  dissolved  in  normal  ace- 
tate, gives  a  sesquibasic  acetate,  which  is  deposited  in 
crystals,  2(Pb2C2H3O2),PbO,II2O. 

GOULARD'S  EXTRACT  is  a  solution  containing  a  mix- 
ture of  normal  and  of  sesquibasic  acetate  of  lead, 
which  is  prepared  by  boiling  30  parts  of  water,  7"  parts 
of  litharge  and  6  parts  of  normal  acetate  of  lead. 

BUTYRIC  ACID. 


It  is  usually  prepared  as  follows:  a  mixture  of 
10  parts  of  sugar,  1  part  of  white  cheese,  10  parts  of  chalk, 
and  some  water,  is  maintained  at  a  temperature  of  30° 
to  35°.  First,  lactate  of  lime  is  formed,  which  causes 
the  mass  to  thicken,  then  that  salt  changes  into  buty- 
rate,  disengaging  hydrogen  and  carbon  dioxide.  When 
the  mixture  has  become  clear,  the  liquor  is  evaporated 
and  the  butyrate  separated  with  a  skimmer.  This 
salt  is  decomposed  by  concentrated  hydrochloric  acid 
which  separates  the  butyric  acid  in  the  form  of  an  oil, 
which  is  distilled  off.  It  boils  at  163°.  It  is  of  a 
fetid  odor,  and  soluble  in  water,  alcohol  and  ether. 


VALERIC    ACID.  109 

YALERIANIC,  OR  VALERIC  ACID  C5H10O2  =     5    9jj  >  O. 

It  can  be  obtained  by  oxjdizing  amjlic  alcohol  by 
a  mixture  of  potassium  bichromate  and  sulphuric  acid? 
or  by  distilling  valerian  root  with  water  acidulated 
with  sulphuric  acid.  The  best  method  is  to  boil  por- 
poise oil  with  water  and  lime.  The  oil  saponifies  and  the 
valerianate  of  calcium  alone  is  dissolved.  This  liquid 
is  concentrated  and  hydrochloric  acid  added  in  excess. 
The  valerianic  acid  separates  out  in  the  form  of  an  oil 
which  is  distilled,  and  that  portion  collected  which 
passes  over  at  175°. 

Pierre  and  Puchot  have  lately  devised  a  process  for 
preparing  valeric  acid  from  amyl  alcohol.  (3— [3]  5-40. ) 

BENZOIC  ACID,  C7H6O2. 

Density,  61. 

Density  of  its  vapor  compared  with  air,  4.27. 

Melts  at  120° ;  boils  at  250°. 

It  is  obtained  by  a  dry,  as  also  by  a  wet  process. 
To  prepare  it  by  the  former  method,  equal  weights  of 
sand  and  gum  benzoin  are  placed  in  an  earthen  ves- 
sel, the  mixture  covered  with  a  sheet  of  filter  paper, 
which  is  pasted  down  round  the  edge,  and  a  long  cone 
of  white  cardboard  placed  over  the  whole.  The 
earthen  vessel  is  then  heated  over  a  slow  fire  for  two 
hours,  and  when  cool  the  cone  is  removed.  The  ben- 
zoic  acid  is  found  to  have  condensed  on  the  interior 
of  the  cone  in  handsome  blades,  or  needles. 


110  ORGANIC    CHEMISTRY. 

It  is  obtained  in  the  wet  way,  by  pulverizing  gum 
benzoin,  mixing  it  with  half  its  weight  of  lime,  and 
boiling  for  half  an  hour  in  a  cast-iron  kettle,  with  six 
times  its  weight  of  water,  care  being  taken  to  agitate 
the  mixture.  It  is  thrown  upon  a  piece  of  linen  and 
the  residue  treated  twice  with  water.  The  liquids  are 
reduced  in  volume  to  two-thirds  that  of  the  water  used 
during  the  first  treatment,  then  saturated  with  hydro- 
chloric acid.  The  benzole  acid  separates  out,  and  is 
recrystallized  from  a  solution  in  boiling  water. 

It  is  also  procured  from  the  urine  of  herbivorous 
animals.  This  secretion,  evaporated  to  a  small  bulk 
and  treated  with  hydrochloric  acid,  yields  a  deposit  of 
hippuric  acid,  which,  on  being  heated  with  dilute  sul- 
phuric acid,  is  transformed  into  benzoic  acid. 

Benzoic  acid  is  also  produced  on  a  large  scale  from 
naphthalin. 

Benzoic  acid  crystallizes  in  lustrous  blades,  or  need- 
les, is  little  soluble  in  cold  water,  quite  soluble  in  boiling 
water,  and  still  more  so  in  alcohol  and  ether.  On 
passing  its  vapors  through  a  tube  heated  to  redness,  it 
is  decomposed  into  benzol  and  carbon  dioxide, 
07H6O2  —  C6H6-f-CO2.  Chlorine,  bromine  and  nitric 
acid  transform  it  into  substitution  products. 

Chlorbenzoic  acid,  C7H5C1O. 
Dinitrobenzoic  "    C7ii4(]S"O2)2O2. 

Ammonium  beazoate  furnishes,  on  distillation,  ben- 
zonitrile  C7NH9O2  -  C7H5K  +  2 FLO. 

The   alkaline   benzoates   heated   with   chloride,   or 


BENZOIO    ACID.  Ill 

oxychloride  of  phosphorus,  furnish  benzyl  chloride, 
which,  submitted  to  the  action  of  potassium  benzoate 
in  excess,  gives  benzoic  anhydride, 

3(KC7H502)+POC13  =  3(C7H5OC1)  +  K3P04. 

Chloride  of  benzyl. 

C7H5OC1+KC7H302  -  C14H1008  +  KCL 

Benzoic  anhydride. 

The   rational   formula   of    benzoic    anhydride    is, 


Calcium  benzoate  heated  to  a  high  temperature 
furnishes  1enzone, 

Ca(C7H502)a=  CaC03+CO(C6H5)2. 

Calcium  benzoate.  Benzone. 

Benzoic  acid  is  monobasic,  and  the  benzoates  are 
generally  soluble.  Benzoic  acid  taken  into  the  stom- 
ach, is  transformed  into  hippuric  acid. 

Kolbe  and  von  Meyer  have  observed  that  benzoic 
acid  has  antiseptic  power,  though  less  than  salicylic 
acid,  (18-[2]12-133). 

CINNAMIO  ACID.  In  certain  balsams  there  exists  an 
acid  called  cinnamic  acid,  whose  formula  is  C9H8O2. 
It  exists  in  the  balsams  of  Peru,  benzoin,  tolu  and  in 
liquid  storax.  It  fuses  at  129°  and  boils  at  290°.  It 


112  ORGANIC     CHEMISTRY. 

lias  striking  features  of  resemblance  to  benzoic  acid, 
and  is  produced  like  the  latter  by  the  oxydation  of  an 
aldehyd.  This  aldehyd  is  the  essence  of  cinnamon 
prepared  by  distilling  cinnamon  with  water. 

POLYATOMIC  ACIDS. 

OXALIC    ACID. 


PREPARATION.  In  the  burdock  and  sorrel  is  found 
an  acid  salt,  commonly  called  salt  of  sorrel,  which  is 
a  mixture  of  binoxalate  and  quadroxalate  of  potas- 
sium. Sodium  oxalate  is  found  in  several  marine 
plants,  calcium  oxalate  in  the  roots  of  the  gentian 
and  rhubarb,  and  in  certain  lichens.  Salt  of  sorrel  is 
extracted  from  the  burdock  (Prunex\  in  Switzerland, 
and  in  the  Black  Forest  of  Germany,  by  expressing 
the  plant,  clarifying  the  expressed  liquid  by 
boiling  with  clay,  and  evaporating  ;  crystals  of  salt  of 
sorrel  are  deposited. 

The  oxalic  acid  may  be  obtained  free  by  decompos- 
ing a  solution  of  these  crystals  with  lead  acetate  ; 
the  oxalate  of  lead  which  precipitates  is  treated  with  a 
suitable  quantity  of  sulphuric  acid  ;  the  lead  is  com- 
pletely precipitated  as  lead  sulphate  ;  this  is  filtered 
off,  and  the  liquid  evaporated  and  allowed  to  crys- 
tallize. 

At  present  this  acid  is  chiefly  prepared  by  t-ie  action 
of  oxydizing  agents  upon  certain  organic  substances; 
the  substances  best  suited  for  this  purpose  are  those 


OXALIC     ACID.  113 

which  contain  oxygen  and  hydrogen  in  the  proportion 
to  form  water.  One  part  of  starch,  or  sugar,  is  boiled 
with  eight  parts  of  nitric  acid  diluted  with  ten 
parts  of  water,  until  nitrous  vapors  cease  to  be  disen- 
gaged, and  the  liquid  then  evaporated.  The  crys- 
tals of  oxalic  acid  which  separate  out  are  freed  from 
the  excess  of  nitric  acid,  by  being  several  times  re- 
crystallized  in  water.  It  is  also  obtained  on  a  large 
scale  by  the  action,  at  a  high  temperature,  of  potassa 
or  soda  on  saw  dust. 

Oxalic  acid  has  been  obtained  synthetically,  by 
Drechel,  on  passing  carbon  dioxide  over  sodium  heated 
to  320°. 


PROPERTIES.  —  Oxalic  acid  crystallizes  in  prisms, 
which  effloresce  in  the  air,  and  which  are  very  soluble 
in  water  and  alcohol. 

It  fumes  at  98°;  at  170°  to  180°  it  is  partially  sub- 
limed, but  the  greater  portion  is  decomposed  into  car- 
bon monoxide,  carbon  dioxide,  formic  acid  and  water. 


Chlorine,  hypochlorous  acid,  fuming  nitric  acid  and 
hydrogen  peroxide,  convert  oxalic  acid  into  carbon 
dioxide. 

Sulphuric  acid  causes  it  to  split  up  into  carbon  mon- 


114  ORGANIC     CHEMISTRY. 

oxide  and  carbon  dioxide,  and  this  reaction  is  made  use 
of  in  preparing  the  former  gas. 

Oxalic  acid  is  bibasic. 

Normal  potassium  oxalate,  K2=O2=CO2 . 
Acid  potassium  oxalate,  KH=O2=C2O2. 

USES. — Oxalic  acid  is  employed  in  removing  ink 
spots  from  cloth,  and  in  cleaning  copper.  It  owes  these 
properties  to  the  fact  that  it  forms  with  iron  and  copper 
soluble  salts,  hence  it  is  also  employed  in  calico-works 
for  removing  colors. 

Toxic  action  of  oxalic  acid.  On  account  of  the  use 
of  oxalic  acid  in  the  arts,  and  its  physical  resemblance 
to  certain  salts,  particularly  to  magnesium  sulphate, 
poisoning  with  it  has  often  occurred,  either  through 
design  or  imprudence. 

It  acts  powerfully  upon  the  system.  Tardieu  men- 
tions the  case  of  a  young  man,  sixteen  years  of  age, 
who  was  poisoned  by  two  grams  of  this  substance. 

The  symptoms  observed  are  similar  to  those  pro- 
duced by  other  corrosive  agents;  great  prostration  fol- 
lowed by  unconsciousness  and  a  persistent  numbness 
in  the  lower  extremities.  The  blood  of  the  patient  be  - 
comes  abnormally  red. 

In  cases  of  poisoning,  the  acid  should  be  removed 
from  the  stomach  with  promptness,  and  milk  of  lime, 
or  magnesium,  or  ferric  hydrate  administered.  Lime 
is  to  be  preferred,  as  it  forms  a  salt  completely  insol- 
uble in  vegetable  acids. 


SUCCINiC    ACID.  115 


SUCCINIC   ACID. 


This  acid  is  produced  by  the  oxydation  of  butyric 
acid,  and  by  subjecting  amber,  succinum,  to  dry  distil- 
lation or  by  the  action  of  iodhydric  acid  on  malic  or 
tartaric  acids. 

Succinic  acid  crystallizes  in  rhomboidal  prisms  which 
melt  at  180°  and  boil  at  about  235°,  at  a  higher  tem- 
perature they  are  decomposed  into  water  and  succinic 
anhydride  C4H4O3.  It  is  soluble  in  5  times  its  weight 
of  cold  water,  soluble  in  ether  and  very  soluble  in  alco- 
hol. 

It  is  used  in  the  artificial  preparation  of  malic  and 
tartaric  acids.  Succinic  acid  has  been  found  in  the 
fluid  of  the  hydrocele  and  ot  certain  hydatids. 

MALIC    ACID. 

C4H3O2  \  ft 
H,II2  f  Us 

This  acid,  discovered  by  Scheele  in  sour  apples,  is 
found  in  many  plants  ;  in  the  berries  of  the  service- 
tree,  in  cherries,  raspberries,  gooseberries,  rhubarb,  to- 
bacco, etc.  Malic  acid  is  levogyrate,  deliquescent 
and  crystallizable;  it  is  soluble  in  alcohol  and  fuses  at 
about  100°. 

At  a  temperature  above  130°,  it  is  decomposed  into 


116  ORGANIC     CHEMISTRY. 

various  acids  and  especially  paramalic  acid,  C4II4O4, 
which  is  identical  with  the  acid  of  the  fumaria.  It 
is  bibasic  like  oxalic  acid,  but  triatomic  and  is  dis- 
tinguished from  this  acid  by  not  producing  a  turbid- 
ity with  calcium  compounds. 

TARTARIC    ACID. 


This  acid,  obtained  from  wine  tartar  by  Scheele,  in 
1770,  occurs  free  and  combined  with  potassium  in 
many  vegetable  products;  in  the  sorrel,  berries  of  the 
service-tree  and  tamarind,  in  the  gherkin,  potato, 
Jerusalem  artichoke,  etc.  The  grape  is  the  chief 
original  source  of  this  acid. 

One  method  of  preparing  tartar ic  acid  is  to  purify 
crude  tartar  by  dissolving  and  clarifying  with  clay, 
which  throws  down  the  coloring  matters:  then  filter- 
ing and  adding  calcium  carbonate,  which  precipitates 
half  of  the  tartaric  acid  as  a  calcium  salt. 

2KHC4H4O6+CaCO3-CiC4H4O6+K2C4H4O6+CO2+H,0 

Hydro-potassic         Calcium    Calcium  tartrate.     Potassium 
tartrate.  carbonate.  tartrate. 

The  solution  which  contains  the  potassium  tartrate, 
is  filtered  and  calcium  chloride  added  :  the  remainder 
of  the  tartaric  acid  is  thus  precipitated  as  a  tartrate 
and  added  to  the  preceding. 


TARTAKIC     ACID.  117 

+  CaCl2=CaC4H406  +  2  KCL 

Potassium  tartrate  Calcium  tartrate. 

These  precipitates  are  washed  and  decomposed  with 
sulphuric  acid,  the  calcium  sulphate  is  filtered  off,  and 
the  liquid  evaporated  to  the  point  of  crystallization. 
This  acid  is  also  called  right  tartaric,  or  dextroracemic, 
as  it  turns  the  plane  of  polarization  to  the  right. 

Kistner  has  obtained  from  certain  tartrates  a  tartaric 
acid  which  is  optically  inactive.  This  acid,  called para- 
tartaric  or  racemic  acid,  is  somewhat  less  soluble  than 
dextrotartaric  acid,  while  the  reverse  is  the  case  with 
its  salts.  It  contains,  moreover,  one  molecule  of  water 
of  crystallization,  but  does  not  crystallize,  as  does  the 
dextrogyrate  acid,  in  hernihedral  crystals. 

Levogyrate  tartaric  acid  is  prepared  by  evaporating 
a  solution  of  racemate  of  cinchonia;  the  levogyrate 
tartrate  precipitates  while  the  dextrogyrate  remains  in 
solution;  or  a  solution  of  racemic  acid  is  allowed  to 
stand  with  a  small  quantity  of  calcium  phosphate,  and 
a  few  spores  of  the  Penoiliuin  glaucum;  fermenta- 
tion sets  in,  which  destroys  the  dextroracemic  acid. 

Dextrotartaric  acid  crystallizes  in  beautiful  oblique 
prisms  with  a  rhombic  base.  Cold  water  dissolves 
twice  its  weight  of  this  acid;  alcohol  dissolves  it  with 
equal  facility.  It  is  insoluble  in  ether. 

Tartaric  acid  melts  at  about  180°;  and  furnishes  dif- 
ferent pyrogenous  acids,  chiefly: 

Tartaric  anhydride,  or  Tartrelic  acid,  C4H4O5,  and 

Pyrotartario  acid,  C5H8O4. 


118  ORGANIC    CHEMISTRY. 

Simpson  synthesized  pyrotartaric  acid  and  Lebedeff 
has  recently  (60-75-100.)  shown,  that  this  acid  is  iden- 
tical with  that  obtained  by  heating  tartaric  acid. 

Tartaric  acid  does  not  precipitate  calcium  salts.  It 
produces  a  turbidity  with  lime  water,  but  an  excess  of 
acid  dissolves  it;  by  these  reactions  it  may  be  distin- 
guished from  malic  and  oxalic  acids. 

TARTRATES.  Tartaric  acid  is  bibasic.  The  two 
tartrates  of  potassium  are  : 

Normal  potassium  tartrate,  E^CJ^Oo 
Hydro  «  «         KC4H5O6. 

This  latter  salt  is  obtained  by  purifying  the  tartar 
of  wine  casks,  and  is  called  cream  of  tartar.  It  is  used 
in  the  preparation  of  black  flux,  white  flux,  potassium 
carbonate,  and  tartaric  acid,  also  largely  in  baking 
powders. 

ROCHELLE  SALT.  KNaCJ^Oe+^aq.  This  salt  is 
a  double  tartrate  of  potassium  and  sodium,  which  was 
formerly  much  used  as  a  purgative.  It  may  be  pre- 
pared by  mixing  in  a  porcelain  dish,  3500  grams  of 
water  and  1000  grains  of  cream  of  tartar,  this  is  brought 
to  boiling  and  sodium  carbonate  added  as  long  as  ef- 
fervescence is  produced.  This  solution  is  then  filtered 
and  evaporated  until  it  has  a  density  of  1.38. 

The  salt  crystallizes  in  regular  rhornboidal  prisms; 
it  is  soluble  in  2J-  times  its  weight  of  water,  but  in- 
soluble in  alcohol. 

TARTAR  EMETIC.     Tartaric  acid  forms,  with  bases,  a 


EMETICS.  119 

a  class  of  salts  called  emetics,  the  type  upon  which 
they  are  formed  being  that  of  tartar  emetic.  The 
ordinary  tartar  emetic  has  been  generally  assigned  the 
formula  (SbO)'K=O2==C4H4O4,  in  which  the  monad 
radicle  stibyl  takes  the  place  of  one  of  the  basic  hydro- 
gen atoms.  It  is  prepared  by  boiling  for  an  hour  in 
100  parts  of  water,  12  parts  of  cream,  of  tartar,  and  10 
parts  of  antimony  oxide.  This  mixture  is  then 
filtered,  evaporated  and  allowed  to  crystallize.  This 
salt  crystallizes  in  rhombic  octahedrons  ;  it  has  a  me- 
tallic taste,  a  slight  acidity,  and  is  soluble  in  Imparts 
of  cold,  and  about  2  parts  of  boiling  water. 

Crystals  of  tartar  emetic  effloresce  on  exposure  to  the 
air. 

A  strip  of  tin  precipitates  the  antimony  as  a  brown 
powder.  Tannin,  and  most  astringents,  precipitate 
the  antimony,  hence  tartar  emetic  should  not  be  ad- 
ministered in  connection  with  this  class  of  bodies. 
This  salt  is  the  most  used  of  the  antimony  compounds. 

FERKO -POTASSIUM  TARTRATE. — Cream  of  tartar  is  di- 
gested with  ferrous  hydrate  for  two  hours  at  a  tem- 
perature of  60°.  For  every  100  parts  of  cream  of  tar- 
tar, a  quantity  of  hydrate  should  be  used  containing  43 
parts  of  ferrous  oxide. 

The  product  is  filtered,  the  liquid  received  in  shallow 
plates,  and  kept  at  a  temperature  of  about  45°;  the  salt 
thus  crystallizes  in  brilliant  scales  of  a  garnet  red  color. 
It  dissolves  in  water,  but  is  insoluble  in  strong  alcohol. 
Tartaric  acid  is  often  adulterated  with  alum,  potassium 
bisulphate  and  cream  of  tartar  ;  these  substances  may 


120  ORGANIC    CHEMISTRY. 

all  be  detected  by  means  of  alcohol,  in  which  they  are 
not  soluble. 

Tartaric  acid  is  used  in  making  effervescing  drinks, 
and  as  a  discharge  by  calico  printers. 

Tartaric  acid  produces  the  same  toxical  effects  as 
oxalic  acid,  though  requiring  much  larger  doses.  The 
blood  of  the  poisoned  person  becomes  red  and  very 
fluid. 

CITRIC     ACID. 


This  acid  is  found  associated  with  oxalic  and  tartaric 
acids  in  many  plants.  It  occurs  in  cherries,  currants, 
raspberries,  oranges  and  lemons. 

It  is  ordinarily  extracted  from  the  juice  of  lemons. 
This  juice  is  allowed  to  stand  until  fermentation  com- 
mences, then  filtered  and  treated  with  chalk  and  milk 
of  lime ;  an  insoluble  citrate  of  calcium  is  formed,  which 
is  decomposed  by  sulphuric  acid;  the  calcium  sul- 
phate is  filtered  off  and  the  filtrate  evaporated  and  left 
to  crystallize.  Citric  acid  crystallizes  in  regular 
rhombic  prisms;  it  is  soluble  in  three  fourths  its 
weight  of  cold  water;  this  solution,  in  time,  becomes 
covered  with  mould. 

Citric  acid  is  soluble  in  alcohol  and  ether.  Heated 
to  about  175°  it  furnishes  aconitio  acid, 

n  TT  n  =  C6H3 


CITKIC    ACID.  121 

losing  H,O  on  increasing  the  temperature.  Another 
pyrogenous  acid,  itaconic  acid  C3H6O4  is  formed, 
which,  if  heated,  is  transformed  into  citraconio  acid 
isomeric  with  the  last  mentioned. 

Oxydizing  bodies  destroy  citric  acid,  carbon  dioxide, 
acetone,  etc.,  being  produced.  Fused  caustic  potassa 
resolves  it  into  acetic  and  oxalic  acids. 

C6H807  +  H20=C2H204 + 2C2H402 . 

Oxalic  acid.  Acetic  acid. 

Citric  acid  is  tetratomic  and  tribasic.  It  may  be 
distinguished  from  oxalic  and  tartaric  acids  by  its  ac- 
tion on  lime  water,  which  it  does  not  precipitate  in  the 
cold,  but  if  boiled  with  an  excess  of  lime  water,  a  pre- 
cipitate of  basic  calcium  citrate  is  obtained. 

MAGNESIUM  CITRATE. — This  salt  is  prepared  by  treat- 
ing magnesium  carbonate  with  a  strong  solution 
of  citric  acid  and  precipitating  this  salt  with  alcohol. 
It  is  much  used  in  medicine  as  a  purgative. 

CITRATE  OF  IKON. — Hydrated  ferric  oxide  is  dissolved 
in  a  hike-warm  solution  of  citric  acid,  and  the  liquid 
evaporated  to  dry  ness. 

This  body  varies  in  its  composition ;  it  occurs  in 
brilliant  amorphous  scales,  of  a  g;irnet-red  color. 

AMMONIA  CITRATE  OF  IRON. — One  hundred  grams 
citric  acid  are  digested  for  some  time  with  a  quantity 
of  ferric  hydrate,  representing  53  grams  of  iron,  and 
16  to  20  grains  of  aqua  ammonia.  The  liquid  is  then 
filtered  and  evaporated  to  the  consistency  of  a  syrup, 


122  ORGANIC     CHEMISTRY. 

and  transferred  to  very  shallow  vessels  which  are 
placed  in  drying  ovens.  This  substance  solidifies  in 
scales,  if  the  temperature  at  which  it  is  dried  is  not  too 
high  and  the  layers  of  liquid  are  extremely  thin. 

LACTIC  ACID. 

03H6O3  =  C3H4 )  O3 
H,H  f  U  ' 

This  acid  was  discovered  by  Scheele,  who  extracted 
it  from  sour  milk.  It  exists  in  many  products  after 
fermentation,  as  sauerkraut,  beet  juice,  and  various 
vegetables,  also  nux  vomica.  It  is  found  in  many  ani- 
mal fluids,  in  the  blood  and  in  the  fluids  which  per- 
meates the  muscular  tissues.  It  is  to  this  body  that  the 
acid  reaction  of  sour  milk  is  due.  Lactic  acid  extracted 
from  flesh  forms,  with  certain  bases,  salts  which  differ 
in  solubility,  etc.,  from  those  formed  with  ordinary 
lactic  acid,  hence  this  acid  is  sometimes  called  paralac- 
tic  acid,  also  sarko-laGtic  acid,  from  Gapnos  flesh. 

Lactic  acid  may  be  prepared  by  dissolving  sugar  of 
milk  in  butter-milk,  adding  chalk  to  the  mixture,  and 
allowing  it  to  stand  for  eight  or  ten  days  at  a  tem- 
perature of  30°  to  35° 

The  sugar  of  milk  is  sometimes  replaced  by  glucose, 
or  cane  sugar  and  fermentation  favored  by  the  addi- 
tion of  cheese. 

A  special  ferment  (tactic  ferment)  is  developed 
which  is  transformed  into  sugar  and  lactic  acid,  but 
the  fermentation  is  arrested  as  soon  as  the  liquid 


LACTIC    ACID.  123 

becomes  acid,  and  it  is  in  order  to  prevent  this  acidity 
that  an  excess  of  calcium  carbonate  or  sodium  bicar- 
bonate is  always  maintained. 

Wurtz  has  produced  this  acid  artificially  by  the 
action  of  platinum  black  on  propylglycol. 

Oa  +  C3II802=C3H603  +  H20. 

Propylglycol. 

Lactic  acid  is  a  colorless,  syrupy  liquid  ;  at  about 
130°  it  is  changed  into  the  anhydride  of  lactic  acid, 
C6H10O5,  and  at  about  250°  it  furnishes  a  crystalline 
body  called  lactide  whose  formula  is  C3H4O2. 

Lactic  acid  posseses  the  property  of  dissolving  cal- 
cium phosphate.  The  lactates  are  soluble  in  water. 
Lactate  of  iron,  (C3H5O3)2Fe,  is  employed  in  medicine. 

UKIC  OR  LITHIC  ACID,  C5H4N4O3. 

Discovered  in  1776,  by  Scheele. 

This  acid  exists  in  human  excretions,  and  in  those  of 
the  carnivora.  In  the  excretions  of  herbivora,  the  uric 
acid  is  replaced  by  hippuric  acid.  Uric  acid  is  present 
in  normal  human  urine  only  in  small  quantity.  The 
urine  of  sedentary  persons,  and  of  those  whose  food  is 
very  nitrogenous  and  quite  substantial,  contains  more 
of  this  substance  than  that  of  individuals  who  lead 
an  active  life,  and  whose  diet  is  less  nourishing.  In 
the  latter  case  the  uric  acid  is  oxydized  and  converted 
into  urea,  hence,  the  proportion  of  the  acid  decreases 
as  the  quantity  of  urea  increases  :  whereas  calculi  of 


124  ORGANIC     CHEMISTRY. 

uric  acid  are  frequently  formed  in  persons  whose  diet 
is  very  nourishing,  and  whose  occupation  necessitates 
but  little  muscular  exertion.  The  excreta  of  birds 
contains  a  large  proportion  of  uric  acid,  and  that  of 
snakes  is  formed  almost  exclusively  of  this  body. 

This  acid  may  be  prepared  by  boiling  a  dilute  al- 
kaline solution  with  guano,  excreta  of  the  boa  con- 
strictor, or  uric  calculi  finely  pulverized. 

The  liquid  is  filtered  and  the  filtrate  supersaturated 
with  hydrochloric  acid ;  the  uric  acid  precipitates  in 
flakes,  which  become  crystalline  on  standing. 

The  author  having  had  occasion  in  1858  to  prepare 
large  quantities  of  uric  acid  from  guano,  found  that  in 
order  to  obtain  the  purest  product,  as  free  from  color- 
ing matter  as  possible,  it  was  preferable  to  use  sod- 
dium  hydrate  as  a  solvent,  and  carbon  dioxide  as  a  pre- 
cipitant, the  latter  in  sufficient  excess  to  transform  the 
hydrate  into  bicarbonate. 

Crystals  of  uric  acid  are  colorless  and  odorless. 
They  are  nearly  insoluble  in  ether  and  alcohol. 
About  1500  parts  of  boiling  water  are  necessary  to 
dissolve  one  part  of  the  acid. 

On  distillation  uric  acid  yields  urea  and  other  cy- 
anic compounds.  Uric  acid  heated  with  water  and 
lead  dioxide  furnishes  urea  and  a  substance  called  al- 
lantoin,  which  has  been  found  in  the  urine  of  sucking 
calves.  Its  formula  is  C4H6N4O3. 

The  same  derivative  of  uric  acid  was  obtained  by 
the  author  in  1858,  also  parabanic  acid,  on  heating  uric 
acid  with  manganese  dioxide  and  sulphuric  acid. 
(80-[2]4:4-218.) 


URIC    ACID.  125 

If  1  part  of  uric  ac*i:l  be  added  to  4  times  its  weight 
of  nitric  acid  of  a  specific  gravity  of  1.45,  the  solution 
being  kept  cool,  small  crystals  of  a  substance  called 
alloxan  separate  out,  whose  formula  is 

C4H4]Sr2O5+3H2O. 

Woehler  and  Liebig  obtained  from  this  body  a  num- 
ber of  very  interesting  derivations,  alloxantin,  al- 
loxanic  acid,  parabanio  acid,  thionuric  acid,  dia- 
luric  acid,  and  finally  a  magnificent  purple  crystalline 
body,  murexide.  A  large  number  of  other  deriva- 
tives have  also  been  obtained  by  other  chemists, 
especially  Bayer.  The  rich  color,  murexide,  is  made 
use  of  in  detecting  uric  acid.  For  this  purpose,  traces 
of  uric  acid  are  heated  in  a  watch  glass  for  a  few 
minutes,  with  one  or  two  drops  of  nitric  acid  ;  the  ex- 
cess of  acid  is  evaporated,  and  the  dry  residue  exposed 
to  the  vapors  of  ammonia,  when  a  purple,  or  very 
beautiful  rose  color,  will  appear. 


HIPPTJKIC  ACID 


The  urine  of  herbivora  contains  a  large  percentage 
of  this  acid,  which  also  exists  in  a  small  quantity  in 
human  urine.  A  frugivoroua  diet  augments  the  pro- 
portion of  this  body.  It  is  prepared  by  boiling  the 
fresh  urine  of  the  horse  (hence  the  name,  from  innos, 
a  horse),  or  better  from  that  of  a  cow,  with  milk  of 


126  ORGANIC    CHEMISTRY. 

lime,  which  is  than  filtered  and  evaporated  to  one- 
tenth  its  volume;  this  is  mixed  with  a  large  excess  of 
hydrochloric  acid  and  left  to.  stand  30  or  12  hours. 
The  impure  hippuric  acid  which  precipitates  is  re-dis- 
solved in  soda  and  re-precipitated  with  hydrochloric 
acid.  Animal  charcoal  may  be  added  to  the  saline  so- 
lution if  the  brown  color  still  remains.  Putrid  urine 
yields  only  benzoic  acid.  Dessaignes  has  prepared 
this  acid  artificially  by  causing  zincic  glycocol  to  act 
on  benzoyl  chloride. 

Zn(C2H4]TO2)2  +  2C7H5OC1= 
+  2C2H3[NH(C7H5O]O2. 


Hippuric  acid  crystallizes  in  colorless  crystals, 
which  require  600  parts  of  cold  water  for  their  solution, 
but  are  very  soluble  in  hot  water  and  alcohol. 

It  is  decomposed  at  240°,  benzoic  and  cyanhydric 
acids  being  found  among  the  products  of  distillation. 
Under  the  action  of  oxydizing  agents  it  furnishes  ben- 
zoic compounds;  with  nitrous  acid  it  yields  benzo-gly- 
colic  acid. 


ALKALOIDS.  127 


ALKALOIDS. 

ARTIFICIAL    BASES  OR    ALKALOIDS. 
PRIMARY. 

CnII2n+3K 

Methylamine  0 

Ethylamine  C2 

Propylamine 

Butylamine  C4Hn!N" 

Amylamine  C5H13N 

Caprylamine  -       C8H19N. 


Acetylamine  C2H5N" 

Allyiaraine  C3H7N. 


Plienylamine,  aniline    -  -     C6H7  N 

Toluidine  C7H9JSr 

Xylidine  -      C8HUN 

Cumidine  -    C9H13K, 

CnH2n_7K 

Phtalidamine        -        -  .  -         C8H9N. 


128  ORGANIC    CHEMISTRY. 


Naphthalamine             -  -      C10H9K 

SECONDARY. 

Dimethylarnine  -      C2H7  JS" 

Methylethylamine     -        -  C3H9  N 

Diethjlamine  -     C4  HnK 

TEKNAEY. 

Trimethylamine  C3H9  N 

Dimethylethylamine  -      C4Hn]N" 

Methylethylamylamine      -  C8H9  N. 

PHOSPHINES. 

Methylphospbine  C  H5  P 

Dimethylphosphine  -     C2H7  P 

Trimethylphosphine    •  C3H9P. 

AESINES. 

Triethylarsine  C6H15As. 

STIBINES. 

Triethylstlbine                    -  C6H15Sb. 


NATURAL    ALKALOIDS.  129 

PKINCIPAL  NATURAL  ALKALOIDS. 

OF    THE    CINCHONAS. 

Quinia,Quinicia  and  QuinidiaC.:oH24]S"2O2 
Cinchonia  and  Cinclionidia  O^EL^O 
Aricina  C^H^NA. 

OF  OPIUM. 

Morphia  C17H19N  O3 

Codeia      -  -     C18H21N  O3 

Thebaia  C19H21JST  O3 

Narcotina  -     O.^H^N  O7 

Papaverine  -                            C2<)H21]S"  O4 

Narceia  - 


OF   THE   STEYCHNOS. 


Strychnia 
Brucia 


OF  THE   SOLANACE^E. 

Nicotina  C10H14N"2 

Atropia    -  C17HaN  O3 

Hyosciamine  CnH^N  O3 

Solania     -  C43HT1K  O16. 

OF    THE    HEMLOCK. 

Conylia  -     C8H15N. 


130  ORGANIC    CHEMISTRY. 

OF   PEPPER. 

Piperidine  C5HnK. 

MISCELLANEOUS. 

Aconitina  -       C27H40N  O 
Yeratria      -  C32H52N2O8 

Theobromine  C7  H8  N4O2 

Caffeia  C8H10N4O2. 

The  first  organic  base  isolated  was  morphia,  obtained 
in  1816,  by  Sertuerner.  In  1819,  Pelletier  and  Ca- 
ventou  extracted  quiriia  from  cinchona  bark,  and  showed 
that  the  very  active  plants  used  in  pharmacy  owed  their 
energy  to  compounds  capable  of  uniting  with  the  acids, 
and  of  forming  with  them  definite  crystallizable  salts. 

From  that  epoch,  the  number  of  organic  alkaloids  has 
become  very  considerably  augmented ;  and  methods 
have  been  discovered  by  which  many  of  the  alkaloids 
are  prepared  artificially.  It  was  Fritsche  who,  in 
1840,  obtained  the  first  artificial  alkaloid  on  distilling 
indigo  with  potassa  ;  he  named  it  aniline.  Gerhard  t 
by  similar  methods  prepared  quinoleine,  Cahonrs 
piperidine,  and  Chantard  toluidine. 

The  distillation  of  organic  matter  also  furnishes  al- 
kaloids. Thus  several  of  them  have  been  obtained 
from  a  product  of  the  distillation  of  bones,  the  oil  of 
Dippel ;  also  as  products  of  the  distillation  of  various 
other  organic  compounds. 


COMPOUND    AMMONIAS.  131 

A  very  general  method  is  due  to  Zinin,  which  con- 
sists in  causing  a  reducing  substance  to  act  upon 
nitrous  compounds  as  nitrobenzol,  for  example.  The 
nitrous  compound  is  introduced  into  an  alcoholic  solu- 
tion of  ammonium  sulphide,  and  the  mixture  allowed 
to  stand;  sulphur  is  soon  deposited,  and  the  hydrogen 
of  the  hydrogen  sulphide  combines  with  the  oxygen 
of  the  nitrous  compound.  Example: 

C6H5NOa  +  3H2S=2H8O  +  3S  +  C6H7N. 

Nitrobenzol.  Aniline. 

For  this  mode  of  reduction,  as  it  is  not  very  prac- 
tical, ar.d  is  tedious  in  execution,  there  is  at  present 
substituted  the  action  of  iron  upon  acetic  acid,  or 
that  of  zinc  or  tin,  on  hydrochloric  acid. 

Wurtz  has  given  a  very  interesting  method,  which  , 
has  led  to  the  discovery  of  alkaloids  much  resembling 
ammonia,  for  that  reason  called  compound  ammonias. 
It  consists  in  causing  potassa  to  react  upon  the  cyanic 
ethers,  these  bodies  being  decomposed  much  like  cy- 
anic acid. 

Thus  methylamine  is  obtained  by  the  action  of 
potassa  upon  cyanate  of  methyl  : 


CO 
™ 


Cyanate  Potassium  Methyl- 

of  methyl.  carbonate.  amine. 

Hofmann   made  known,  very  shortly  after  the  pub- 


132  ORGANIC     CHEMISTRY. 

lication  of  Wurtz'  process,  a  method  for  the  prepara- 
tion of  the  compound  ammonias,  by  which  not  only  a 
simple  equivalent  of  hydrogen  is  replaced  by  the 
radicles  (CH3),  (G,H5),  etc.,  but  all  the  hydrogen  of 
the  ammonia.  Hof maim' s  method  consists  in  causing- 

o 

ammonia  to  react  upon  hydrochloric  as  well  as  brom- 
liydric  or  iodhydric  ethers,  particularly  the  latter. 

Let  us  take,  as  an  example,  iodide  of  ethyl  in  con- 
nection with  the  study  of 

ETHYLAMINE. 

Ten  to  15  grams  of  iodide  of  ethyl  and  50  grams  of 
aqua  ammonia  are  heated  in  sealed  tubes  of  green  glass 
placed  in  a  water  bath.  The  following  reaction  occurs: 

C2II5I  +  OTI3= Q,H8NI. 

When  the  liquid  has  become  homogeneous  it  is 
allowed  to  cool,  then  decomposed  by  a  solution  of  po- 
tassium hydrate,  the  vapors  being  collected  in  water, 
containing  hydrochloric  acid.  The  hydrochloric  acid 
solution  is  evaporated  to  dryness,  and  the  residue  treated 
with  pure  alcohol,  which  dissolves  the  chlorhydride  of 
ethylamine  and  leaves  in  an  insoluble  state  the  ammo- 
nium chloride  derived  from  the  excess  of  ammonia 
used.  The  solution  of  chlorhydride  of  ethylamine  is 
evaporated  to  dryness,  and  the  deliquescent  crystals 
obtained  decomposed  by  potassium  hydrate,  with  the 
aid  of  a  gentle  heat.  The  volatilized  product  is  con- 
densed in  a  cooled  receiver.  In  this  reaction  there  is 


CLASSIFICATION  OF  THE  ALKALOIDS.       133 

also  formed  diethylamine,  triethylamine  and  oxide  of 
tetrethylammonium  from  which  the  ethylamine  is 
separated  by  distillation. 

It  may  be  obtained  more  readily  by  first  distilling 
1  part  potassium  cyanate  with  2  parts  potassium 
mlphovinate,  then  by  decomposing  the  cyanic  ether 
obtained  with  a  boiling  solution  of  potassium  hydrate 
contained  in  a  flask  connected  with  a  cool  receiver. 

Ethylamine  is  a  limpid  liquid,  with  a  strong  odor 
resembling  that  of  ammonia.  It  has  not  been  solidi- 
fied. It  boils  at  18.7°,  and  dissolves  in  water,  producing 
a  very  caustic  solution.  Ethylamine  is  equally  soluble 
in  alcohol  and  ether.  It  is  combustible,  burning  with 
a  blue  flame,  yellow  at  the  margin. 

It  displaces  ammonia  from  its  combinations.  Its 
solutions  give  reactions  similar  to  those  of  ammonia; 
for  instance,  with  salts  of  copper  it  gives  a  bluish  white 
precipitate,  which  is  dissolved  in  an  excess  producing 
a  deep-blue  solution. 

It  differs  from  ammonia  in  the  following  reaction: 
ethylamine  precipitates  alumina  from  its  salts,  and 
the  precipitate  is  soluble  in  an  excess  of  ethylamine, 
which  is  not  the  case  with  ammonia. 

CLASSIFICATION   OF     THE     ALKALOIDS,   OE   ORGANIC     BASES. 

AMINES. — Hofmann  has  given  the  names  of primary 
amines,  or  monamines,  to  ethylamine,  which  we  have 
just  studied,  and  the  compound  ammonias  in  which  a 
single  atom  of  hydrogen  has  been  replaced  by  a 
radicle. 


134  ORGANIC     CHEMISTRY. 

The  same  chemist,  having  prepared  ethylamine  by 
the  action  of  ethyl  iodide  upon  ammonia,  subse- 
quently succeeded  in  obtaining  diethylamine  by  similar 
means. 

The  reaction  is  the  following  : 

(  C2H5  (  C2H5 

NlH     +C2HJ=]^  C3H8,HL 
(H  (H 

This  hydroiodide  obtained,  treated  with  potassium 
hydrate  or  lime,  furnishes  a  second  base,  which  is 
biethylammonia,  or  diethylamine  ; 


Diethylamine  C 
A  similar  compound  is, 


C6H5 
Ethylaniline  Cs^N^N  1  C2H5. 


These  bases  have  been  given  the  name  of  secondary 
amines  or  imides. 

The  secondary  ammonias  are  attacked  by  ethyl  iodide 
and  other  ethers,  and  a  reaction  takes  place,  iden- 
tical with  that  which  gives  rise  to  the  primary  and 
secondary  amines  and  tertiary  amines,  also  called 
nitrile  bases,  are  thus  obtained. 


AMINES.  135 

Such  bodies  are: 

PC2H5 
Triethylamine  C6II15]N'=E"-[  C2H5. 

L  QzH-s 

fCH3 

Methylethylphenylamine  CgHigN^N-j  C2H5 

LC6H5 

These  bases  are  related  to  the  alcohols  in  the  same 
manner  as  the  primary  amines.  Thus  diethylamine  is 
derived  from  the  action  of  2  molecules  of  alcohol  on  1 
molecule  of  ammonia  and  the  elimination  of  2  mole- 
cules of  water: 

2(C2H6O)  +  NH3—  2H2O=C4HnK 

In  like  manner  the  ternary  amines  may  be  consid- 
ered as  derived  from  3  molecules  of  alcohol  and  1  mole- 
cule of  ammonia  with  the  elimination  of  3  molecules 
of  water. 

There  are  also  bodies  built  upon  the  type  of  two 
and  three  condensed  molecules  of  ammonia,  and  are 
denominated,  respectively,  di-  amines  and  tri-amines;  as 

(  (02H4)" 
Secondary  ethylene  diamine  N2  •<  (C2H4)", 


Ternary  ethylene  diamine  Nz  \  (GJL)". 


136  ORGANIC    CHEMISTRY. 

Triethylamine  attacks  hydroiodic  ether,  and  there  is 
formed  the  compound  C8H2Q1STI=]S"(C2H5)4I.  This 
body  treated  with  oxide  of  silver,  furnishes  an  oxy- 
genated quaternary  base, 


^lSri  +  Ag  HO=Ag  I  +  C8H21NO. 


This  substance  is  very  caustic,  soluble  in  water  and 
acts  as  an  inorganic  alkaline  base  like  potassium 
hydrate,  with  which  body  it  is  also  analagous  in  com- 
position. 


o 


AMIDES,  ALKALAMIDES. — The  amides  are  bodies  built 
upon  the  type  of  ammonia,  in  which  one  or  more  of  the 
hydrogen  atoms  are  replaced  by  an  acid  compound 
radicle;  thus, 


acetamide  1ST 


There  are  also  mixed  combinations  of  amides  and 
amines,  called  alJcalamides,  as 

0,H, 

acetanilide  X  •!  C2H3O. 
H 


ALKALOIDS.  137 


NATURAL  ALKALOIDS. 

Many  of  the  natural  alkaloids  appear  to  possess  a 
composition  analogous  to  that  of  the  compound  am- 
monias. Some  -are  not  attacked  by  iodide  of  ethyl, 
and  should  be  classified  among  the  ammoniums,  bodies 
having  the  same  relation  to  the  compound  ammonias 
as  does  ordinary  ammonium  hydrate  to  ammonia. 
Others  are  acted  upon  by  iodide  of  ethyl,  and,  from  the 
number  of  bases  furnished,  it  may  be  ascertained 
whether  they  belong  to  the  primary,  secondary  or  ter- 
nary compound  ammonias. 

The  properties  of  the  natural  alkaloids  in  general, 
resemble  those  of  the  artificial  bases  or  alkaloids. 
They  contain  nitrogen ;  those  that  do  not  contain  oxy- 
gen are  ordinarily  volatile,  while  those  with  oxygen  are 
non- volatile ;  they  are  very  soluble  in  alcohol,  ether 
and  chloroform. 

Certain  ones  are  dissolved  by  the  hydrocarbides, 
which  are  now  considerably  used  in  the  preparation  of 
the  alkaloids.  Water  does  not  dissolve  any  of  the 
artificial  alkaloids,  except  those  having  a  very  low 
molecular  weight,  like  ethylainine;  this  liquid,  how- 
ever, dissolves  cod eia  and  narceia  quite  readily.  With 
the  exception  of  quinia  and  cinchonia,  they  turn  the 
plane  of  a  polarized  ray  of  light  to  the  left. 

They  react  like  ammonia,  or  potassa,  with  vegetable 


138  OEGANiC    CHEMISTRY. 

colors,  and  furnish,  with  platinum  bichloride,  crystal- 
lizable  double  chlorides,  little  soluble  and  yellow  in 
color.  They  combine  equally  well  with  auric  and  mer- 
curic chlorides. 

The  natural  alkaloids  have  ordinarily  a  bitter  taste. 
Among  their  salts  the  sulphates,  nitrates,  chlorides 
and  acetates  are  mostly  soluble,  while  the  oxalates, 
tartrates  and  tannates  are  insoluble. 

The  harmless  character  of  tarmic  acid,  and  the  in- 
solubility of  the  compounds  formed  by  it,  with  the  al- 
kaloids, render  tannin  and  astringent  vegetable  sub- 
stances generally  very  efficacious  antidotes. 

The  precipitates  they  produce  are  soluble  in  acid  and 
alkaline  liquids. 

The  alkaloids  are  partially  precipitated  from  their 
solutions  by  potassa,  soda  and  ammonia.  Iodine  water 
and  solutions  of  iodine  in  potassium  iodide,  precipitate 
them  completely. 

According  to  Schultze,  the  liquid  obtained  by  add- 
ing antimony  perchloride  to  a  solution  of  phosphoric 
acid,  is  a  re-agent  which  precipitates  most  of  the  or- 
ganic bases. 

A  delicate  re-agent  for  the  alkaloids  is  the  double 
iodide  potassium  and  mercury.  According  to  Meyer, 
the  best  proportions  are  49  grams  of  potassium  iodide 
and  135  grams  of  mercury  di chloride,  to  1  litre  of 
water.  It  is  best  to  add  the  re -agent  to  the  solution 
of  the  alkaloid,  which  may  be  neutral,  acid,  or  even 
feebly  alkaline. 

It   must  be  borne  in  mind   that   the   presence  of 


NICOTINA.  139 

sugar,  tartaric  acid  and  of  albumen  may  mask  the  reac- 
tions of  a  number  of  alkaloids. 

NICOTINA   OR   NICOTYLIA. 


Nicotina  is  obtained  from  tobacco  (Nicotina  taba- 
cwm.)For  this  purpose  a  decoction  of  tobacco  is  made, 
and  the  liquor  evaporated  to  a  syrup.  The  extract  is 
treated  with  twice  its  volume  of  85  per  cent,  alcohol, 
which  precipitates  the  salts  present  and  certain  organ- 
ic substances. 

The  alcoholic  solution  is  distilled  and  the  residue 
submitted  to  a  second  similar  treatment.  The  alco- 
holic extract  thus  obtained,  is  mixed  with  a  concen- 
trated solution  of  potassium  hydrate,  and  the  nicotina 
liberated  is  re-dissolved  in  ether.  This  ethereal  solu- 
tion is  evaporated  in  a  water  bath,  and  the  residue 
distilled  in  an  oil  bath,  in  an  atmosphere  of  hydrogen. 

Nicotina  is  a  colorless  liquid  when  pare,  remaining 
liquid  at  -10°,  boiling  at  about  2±5°,  with  decomposi- 
tion. It  has  the  odor  of  an  old  pipe.  Exposed  to 
the  air  it  becomes  brown,  then  resinous;  water,  alcohol 
and  ether  dissolve  it  ;  its  solutions  are  strongly 
levogyrate. 

Nicotina  is  a  powerful  base;  it  fumes  when  a  rod 
moistened  with  hydrochloric  acid  is  brought  near  it  ; 
it  precipitates  the  metallic  oxides.  Nicotina  requires 
two  molecules  of  a  monobasic  acid  for  saturation. 
The  chloride,  CioIIuN^IICl,  is  crystallizable,  though 


140  ORGANIC     CHEMISTRY. 

deliquescent.  The  hydrogen  it  contains  is  not  replace- 
able by  methyl,  ethyl,  etc.  It  may  be  considered  as 
having  the  rational  formula, 


(C5H7y  '  '  being  the  compound  radicle  nieotyl. 
Proportion  of  nicotina  in  different  tobaccos  : 

Havana,  2.0  per  ct. 

Maryland,  2.3      " 

Virginia,  6.9      " 

Lothringen,  8.0      " 

(Schloesing.) 

POISONING    BY   TOBACCO   OK    BY    NICOTINA. 

The  injection  of  a  concentrated  decoction  of  tobacco, 
causes  serious  results  in  a  few  minutes  :  intense  head- 
ache is  produced,  with  nausea  and  vomiting,  violent 
pain  in  the  abdomen,  pallor,  and,  finally,  extreme 
prostration. 

An  infusion  of  tea,  unroasted  coffee,  or  any  astring- 
ent substance  (pulverized  nut-galls,  or  oak-bark)  are 
the  only  antidotes  known,  and  they  are  far  from  being 
wholly  reliable. 

The  pure  nicotina  is  -one  of  the  most  dangerous 
poisons.  It  manifests  itself  immediately  on  being 
taken,  since  it  is  entirely  soluble  in  water. 

The  nervous  system  is  especially  affected.  Two  or 
three  drops  suffice  to  cause  death. 


CONIA.  141 

Two  drops  introduced  into  the  throat  of  a  dog  will 
almost  instantaneously  cause  the  following  series  of 
symptoms  :  respiration  becomes  difficult,  the  animal 
staggers,  falls  without  the  power  of  rising  again, 
throws  the  head  back  and,  in  a  few  moments,  is  perfect- 
ly paralyzed,  and  death  ensues. 

PIPERIDINE. 


There  has  been  obtained  from  the  pepper  (  Piper 
longum,  Piper  nigrum  or  Piper  caudatum\  a  body 
crystallizing  in  colorless  prisms  called  piperine,  whose 
formula  is  C17H19NO3.  It  is  a  neutral  substance. 
"When  distilled  with  three  times  its  weight  of  soda- 
lime  it  furnishes  piperidine,  a  limpid  liquid  having 
the  taste  of  pepper,  and  also  its  odor,  soluble  in  water 
and  alcohol,  boiling  at  106°. 

This  body  is  alkaline  and  saturates  acids.  It  con- 
tains a  single  atom  of  hydrogen  replaceable  by  methyl, 
ethyl,  etc. 

CONIA,   CONYLIA,  OR  CONINE. 

08H15N. 

This  body  is  obtained  from  hemlock  (Conium  mac- 
idatum);  the  crushed  seeds  are  distilled  in  a  large  glass 
retort,  with  a  solution  of  potassa,  or  soda,  whereupon  an 
alkaline  distillate  is  obtained.  The  distilled  product  is 
treated  with  a  mixture  of  two  parts  of  alcohol  and  one 


142  OKGAISTIC     CHEMISTRY. 

part  of  ether,  which  dissolves  the  sulphate  of  coniaand 
leaves  the  insoluble  sulphate  of  ammonium.  The  ethe- 
real alcohol  is  separated  by  distillation,  potassa  is  added 
to  the  residue,  and  the  mixture  distilled.  Water  and 
eonia  pass  over;  the  latter  is  dehydrated  with  po- 
tassa, and  rectified  in  vacua,  or  in  a  current  of  hydro- 
gen gas. 

Conia  is  a  colorless,  oily  liquid;  emitting  an  odor 
of  hemlock.  Water  dissolves  it  but  little,  and  this 
better  when  cold  than  warm.  It  is  very  soluble  in  al- 
cohol and  ether.  It  boils  at  about  210°,  yet  emits  va- 
pors even  when  cold,  for  if  a  glass  rod,  moistened  with 
hydrochloric  acid,  is  brought  near  it,  white  fumes  are 
produced.  It  is  a  monacidic  base,  very  alkaline,  and 
forms  crystallizable  salts.  One  of  its  atoms  of  hydro- 
gen is  replaceable  by  ethyl  or  methyl. 

This  base  is  very  poisonous.  According  to  Christi- 
ason,  ten  centigrams  would  suffice  to  cause  death.  It  is 
classified  among  the  narcotics;  its  action  is  charac- 
terized particularly  by  its  effect  on  the  organs  of  respi- 
ration and  the  left  ventricle  of  the  heart. 

ALKALOIDS   OF   THE    PAP  AVERAGES. 

The  seeds  of  the  poppy  (Papaver  somniferwn} 
yield,  on  incision,  a  milky  sap,  which  dries  up  in  a  day 
or  two;  this  sap,  when  solidified,  constitutes  opium. 
There  are  three  leading  varieties  of  opium  : 

I.  Opium  of  .Smyrna  is  found  in  small  cakes  of 
100  to  150  grams,  frequently  distorted  and  agglutinated 
together  by  reason  of  their  soft  nature,  and  contain  >l 


OPIUM.  143 

to  10  per  cent,  of  water.  The  surface  is  brown,  but  the 
interior  has  a  fawn  color.  Sometimes  it  is  found  to 
contain  14  to  15  per  cent,  of  morphia,  but  in  other  in- 
stances only  5  to  6.  Good  Smyrna  opium  should  con- 
tain not  less  than  10  per  cent. 

II.  The  opium  of  Constantinople  is  drier  than  the 
preceding.     It  appears  in  commerce  in  flattened,  irreg- 
ular cakes,  almost  always    surrounded   with  poppy- 
leaves.     It  contains  5  to  10  per  cent,  of  morphia. 

III.  The  opium  of  Egypt  is  still  dryer ;  it  is  rarely 
enveloped  in  leaves.     Its  odor  is  feeble,  and  it  contains 
no  more  than  2  to  7  per  cent,  of  morphia. 

Recently,  attempts  have  been  made  to  cultivate  the 
poppy  in  Europe,  especially  in  France. 

Opium  contains  the  alkaloids  morphia,  codeia,  the- 
beia,  papaverine,  opianine,  narcotine  and  narceia,  an 
acid  combined  with  these  alkaloids  called  meconic  acid 
(from/n/KCtfr,  a  poppy),  a  crystallized  neutral  substance 
called  meconine,  which,  according  to  Berthelot,  is  a 
complex  alcohol,  and  finally,  various  gummy  and  resin- 
ous compounds. 

MORPHIA    OR    MORPHINE. 

C17H19N03,H20. 

PREPARATION.  Ten  kilos,  of  opium  are  treated  re- 
peatedly with  water,  and  the  liquors  evaporated  to  the 
consistency  of  a  syrup. 

The  mass  is  redissolved  in  water,  filtered,  and  again 
evaporated.  To  the  lukewarm  liquid  are  added  1200 


144  ORGANIC    CHEMISTRY. 

grams  of  anhydrous  calcium  chloride,  dissolved  in 
twice  its  weight  of  water.  A  complex  precipitate  is 
formed,  containing  resins,  coloring  matters,  and  sul- 
phate and  meconate  of  calcium,  which  is  thrown  upon 
a  filter. 

The  filtered  liquid  is  evaporated  over  a  water  bath. 
During  the  concentration,  a  fresh  quantity  of  meconate 
of  calcium  is  separated  by  filtering,  and  the  liquid 
evaporated  to  the  consistency  of  syrup.  The  liquid  is 
then  acidulated  with  a  small  quantity  of  hydrochloric 
acid,  and  set  aside  in  a  cool  place. 

At  the  end  of  a  few  days,  it  contains  brown  crystals 
of  the  double  cblorhydrate  of  morphia  and  codeia,  con- 
taminated with  a  blackish  liquid;  these  crystals  are 
drained,  pressed,  and  again  dissolved  in  as  little  boil- 
ing water  as  possible.  The  chlorhydrate,  on  cooling, 
deposits  crystals,  which  are  again  dissolved  in  hot 
water  and  decolored  with  animal  charcoal.  After 
heating  to  80°  or  85°,  the  solution  is  filtered,  and  the 
liquid,  on  being  concentrated,  deposits  the  double  chlor- 
hydrate  in  pure  white  crystals. 

This  salt  is  again  dissolved  in  boiling  water,  and  the 
hot  liquid  treated  with  ammonia  ;  the  codeia  remains 
in  solution,  while  the  morphia  is  precipitated.  This 
deposit  is  thrown  upon  a  filter  washed  with  cold  water, 
dried,  and  dissolved  in  boiling  alcohol ;  the  morphia 
separates  out  in  crystals  on  cooling. 

It  frequently  contains  some  narcotina,  from  which 
it  is  freed  by  washing  once  or  twice  with  ether,  or 
chloroform,  which  dissolves  the  narcotina,  and  does 
not  aifect  the  morphia. 


MORPHIA.  145 

Pure  morphia,  (from  Morpheus,  in  allusion  to  its  nar- 
cotic qualities,)  crystallizes  in  regular  prisms  with  a 
rhombic  base,  is  colorless,  soluble  in  500  parts  of  boil- 
ing water,  scarcely  soluble  in  cold.  Forty  to  forty-five 
parts  of  cold  90  per  cent,  alcohol  are  required  to  dis- 
solve one  part  of  morphia ;  it  is  insoluble  in  ether. 
Solutions  of  morphia  are  very  bitter. 

Morphia  is  little  soluble  in  ammonia,  while  it  is  dis- 
solved very  readily  by  alkaline  solutions,  and  even  by 
lime  water. 

Under  the  action  of  heat,  it  fuses  in  its  water  of 
crystallization,  the  latter  escaping,  and  the  alkaloid  re- 
crystallizes  on  cooling. 

Morphine  is  an  energetic  reducing  agent,  reducing 
gold  and  silver  salts,  setting  free  the  respective  metals. 
It  separates  the  iodine  from  solutions  of  iodic  acid. 
If  a  solution  of  starch  is  poured  into  a  test-tube,  and  a 
solution  of  iodic  acid  and  traces  of  morphia  added,  the 
blue  color  of  iodide  of  starch  appears. 

If  morphia  is  put  into  a  few  drops  of  a  concentrated 
and  slightly  acid  solution  of  a  ferric  salt,  a  beautiful 
blue  color  is  produced,  which  subsequently  changes  to 
green. 

Morphia,  moistened  with  nitric  acid,  is  colored 
orange-red,  which  rapidly  changes  to  yellow. 

These  four  reactions  are  characteristic  of  morphia. 

If  iodine  and  morphia  are  mixed  in  equal  propor- 
tions and  the  mixture  treated  with  boiling  water,  a 
brown  liquid  is  formed  which  deposits  a  reddish-brown 
powder  called  iodomorphia.  Morphia  fused  with  al- 


146  ORGANIC     CHEMISTRY. 

kalies  yields  methylamine.  (p.  127")..  It  is  attacked  by 
ethyl  iodide  at  100°,  a  single  molecule  of  ethyl 
entering  into  the  group. 

Morphia  forms  crystallizable  salts,  from  the  solutions 
of  which  it  is  precipitated  by  the  fixed  alkalies. 

CHLORHYDRATE  OF  MORPHIA,  C17H19NO3HC1+3II2O. 
To  prepare  this  salt,  100  parts  of  pulverized  morphia 
are  treated  with  a  little  warm  water,  then  hydrochloric 
acid  is  added  in  sufficient  quantity  to  dissolve  the  al- 
kaloid. The  solution  is  afterwards  evaporated  in  a 
water  bath  until  it  crystallizes. 

This  salt  is  soluble  in  20  parts  of  cold  water,  very 
soluble  in  alcohol.  It  is  the  salt  of  morphia  most 
used,  and  contains  Y6  per  cent,  of  morphia. 

SULPHATE  OF  MORPHIA,  (C^H^NOg^HoSC^+SILjO 
is  prepared  like  the  preceding  salt,  which  it  resembles 
in  appearance  as  well  as  in  properties. 

Morphia  and  its  salts  are  used  in  very  small  doses, 
as  in  larger  doses  they  are  energetic  poisons. 

CODEIA,  CisH^JSTOsilljO. 

Discovered  in  1832  by  Robiquet.  This  base,  whose 
name  is  derived  from  xGddrj  poppy  head,  exists  in  the 
ammoniacal  solution  obtained  in  the  preparation  of 
morphia.  On  evaporation  the  ammonia  is  driven  off 
and  the  codeia  is  precipitated  by  potassa.  The  codeia 
is  at  first  precipitated  in  the  form  of  a  sticky  mass 
which  soon  becomes  pulverescent.  It  is  washed  with 
and  dissolved  in  hydrochloric  acid.  The  liquid  is  then 
boiled  with  washed  animal  charcoal,  and  the  codeia 
precipitated  with  potassa. 


NAKCOTINA.  147 

Codeia  is  crystalline,  very  soluble  in  alcohol  and 
ether.  It  dissolves  in  80  parts  of  cold  and  in  20  parts 
of  boiling  water. 

o 

Codeia  is  very  soluble  in  ammonia,  and  nearly  in- 
soluble in  potassa.  With  chlorine,  bromine  and  ni- 
tric acid  it  forms  products  of  substitution.  With 
iodine  it  furnishes  ruby-red  crystals,  whose  formula  i& 

C18H21]TO3L 

Codeia  is  somewhat  used  as  an  anodyne.  It  is  easily 
distinguished  from  morphia,  since: 

I.  Codeia  is  soluble  in  ether  and  ammonia. 

II.  It  is  insoluble  in  solutions  of  potassa. 

III.  It  does  not  reduce  iodic  acid  or  ferric  salts. 
IY.  Nitric  acid  does  not  impart  to  it  any  color. 


NAKCOTINA, 

Narcotina  crystallizes  in  rhombic  prisms.  It  is  al- 
most insoluble  in  cold  water,  somewhat  soluble  in 
alcohol,  quite  so  in  ether.  It  fuses  at  170°,  and  is 
decomposed  before  reaching  200°.  Dilute  nitric  acid 
transforms  it  into  various  products  of  oxydation,  the 
most  important  of  which  are  meconine,  cotarnine 
and  opianic  acid  Narcotina  unites  with  acids,  but 
the  compounds  are  decomposed  on  evaporation. 

It  is  distinguished  from  morphia  in  that  it  does  not 
reduce  iodic  acid  and  ferric  salts,  and  from  codeia  in 
giving  with  nitric  acid  a  blood  red  coloration.  This 
substance  is  also  insoluble  in  potassa  and  ammonia. 
It  is  not  as  poisonous  as  morphia. 


148  ORGANIC    CHEMISTRY. 


THEBAIA. 


This  alkaloid,  sometimes  called  paramorpliicb,  is  the 
most  poisonous  of  the  bases  of  opium. 

It  is  crystallizable,  insoluble  in  water,  soluble  in 
alcohol  and  ether.  Fuming  nitric  acid  attacks  it  in 
the  cold,  and  a  yellow  liquid  is  obtained,  which  be- 
comes brown  on  contact  with  alkalies,  and  which  dis- 
engages an  alkaline  vapor.  Concentrated  sulphuric 
acid  gives  it  a  red  hue. 

PAPAVERINE. 


This  body  is  crystallizable,  insoluble  in  water,  quite 
soluble  in  boiling  alcohol  and  ether.  It  forms  crystal- 
line salts. 

Under  the  action  of  strong  sulphuric  acid  it  as- 
sumes a  deep  blue  color,  though  Hesse  and  Drag- 
eridorff  have  recently  ascertained  that  when  absolutely 
pure  no  color  is  obtained,  the  ordinary  article  found 
in  trade  not  being  pure. 

NARCEIA. 


This  alkaloid,  crystallizes  in  silky  needles,  insoluble 
in  ether,  soluble  in  alcohol  and  boiling  water,  little 
.soluble  in  cold  water.  It  forms  crystallizable  salts. 


OPIUM.  149 

Narceia  fuses  at  95°,  and  commences  to  decompose 
at  about  110°.  It  is  attacked  in  the  cold  by  concentrated 
sulphuric  acid,  a  red  liquid  being  produced  which 
rapidly  becomes  green,  especially  if  slightly  heated. 
The  best  means  of  distinguishing  narceia  is  to  cause  a 
solution  of  iodine  to  act  upon  the  pulverized  substance. 
According  to  Roussin,  the  operation  is  most  easily  per- 
formed with  one  part  of  iodine  and  two  parts  of  potas- 
sium iodide  dissolved  in  ten  parts  of  water.  A  blue 
color  is  produced,  which  disappears  on  coming  in  con- 
tact with  alkalies,  or  on  heating. 

PHYSIOLOGICAL  ACTION  OF  OPIUM.       NARCOTIC  POISONS. 

Opium  in  small  doses  is  a  very  highly-prized  ano- 
dyne. Continued  use  of  this  substance  produces  a 
peculiar  state  of  inebriation,  an  excited  sleep  and  hal- 
lucinations of  various  sorts. 

The  bodies  of  opium-eaters  are  lean  and  cadaverous, 
their  eyes  are  lustrous,  their  forms  bent;  their  appe- 
tite diminishes,  and  they  exist  only  by  increasing  the 
dose  of  the  poison  which  destroys  them.  In  larger 
doses  it  is  highly  poisonous,  and  acts  in  a  different 
manner  from  that  of  the  poisons  already  studied.  It 
may  be  considered  as  the  type  of  the  narcotic  poisons. 
It  is  not  unfrequently  used  for  criminal  purposes, 
and  the  imprudent  administration  of  laudanum  and 
other  solutions  of  this  substance  often  causes  serious 
effects. 

Claude  Bernard  has  made  a  careful  study  of  the  ac- 
tion of  the  various  alkaloids  of  opium  upon  the  system, 


150 


ORGANIC     CHEMISTRY 


and  has  tabulated  their  soporific,  toxic,  and  convulsive 
actions  as  follows  : 


Toxic. 

Thebeia, 
Codeia, 
Papaverine, 
ISTarceia, 
Morphia, 
Narcotina. 

Convulsive. 

Thebeia, 
Papaverine, 
Narcotina, 
Codeia, 
Morphia, 
Nareeia, 

Soporific. 

Narceia, 
Morphia, 
Codeia. 

With-    ) 

out     V 

action.    ( 

Those  at  the  head  of  each  column  are  the  most 
marked  in  the  respective  characteristic  action. 

Subjoined  are  tabulated  the  principal  chemical 
characteristics  of  the  opium  alkaloids  : 


WATER. 

ALCOHOL. 

ETHER. 

AMMONIA. 

Morphia. 

But  little   sol- 
uble. 

Quite  soluble. 

Almost    insol- 
uble. 

Nearly    insol- 
uble. 

Codeia. 

Soluble. 

Very  soluble. 

Very  soluble. 

Soluble. 

Narcotina. 

Insoluble. 

Soluble. 

Soluble. 

Insoluble. 

Thebeia. 

Insoluble. 

Soluble. 

Soluble. 

Insoluble. 

Papaverine. 

Insoluole. 

Soluble. 

Soluble. 

Insoluble. 

Narceia. 

Slightly  sorble 

Soluble. 

Insoluble. 

Insoluble. 

QUINIA. 
QUINIA   OR   QUININE. 


151 


This  alkaloid  was  discovered  in  1820  by  Pelletier 
and  Caventou.  The  following  is  the  modern  process 
by  which  it  is  prepared. 

Yellow  Peruvian  bark  is  carefully  pulverized  and 
thoroughly  mixed  with  30  per  cent,  of  its  weight  of 
lime,  previously  slacked.  The  mass  is  then  lixiviated 
three  or  four  times  with  refined  petroleum  (petroleum 
ether)  or  amylic  alcohol,  (wood  spirit)  which  dissolves 
the  alkaloids. 


POTASSA. 

NITRIC   ACID. 

SULPHURIC    ACID. 

IODIC  ACID. 

Soluble. 

Orange-red     color- 
ation. 

Colored  violet  on 
heating  with  di- 
lute acid. 

Reduced. 

Nearly  insoluble. 

Orange-red     color- 
ation, 

Colored  violet  on 
heating  with  di- 
lute acid. 

Is  not  reduced. 

Insoluble. 

Blood  -red     color- 
ation. 

Yellow  coloration. 

Is  not  reduced. 

Insoluble. 

Yellow  coloration. 

Red  coloration. 

Insoluble. 

Dark  -blue  color- 
ation. 

Insoluble. 

Red  color,  which 
becomes  green. 

152  ORGANIC     CHEMISTRY 

The  united  extracts  are  agitated  with  water,  acidu- 
lated with  sulphuric  acid,  making  the  liquid  only 
slightly  acid. 

When  the  solution  is  completed,  animal  charcoal  is 
added,  and  the  liquid  brought  to  boiling,  filtered  while 
still  hot,  and  allowed  to  cool.  The  quinia  sulphate 
which  is  formed,  S^^B^NgC^),  H2SO4-|-7aq.,  being 
but  slightly  soluble,  is  deposited  on  cooling. 

After  being  allowed  to  stand  24  hours,  the  sulphate 
is  collected,  expressed  and  redissolved  in  as  small  a 
quantity  of  water  as  possible,  containing  a  few  drops 
of  sulphuric  acid. 

The  liquid  on  cooling,  deposits  crystals,  which  are 
dried  at  35°.  The  mother  liquors  are  treated  with 
ammonia,  or  sodium  carbonate,  which  precipitates  a 
certain  quantity  of  the  alkaloid.  The  precipitate  is 
lightly  washed  with  water,  redissolved  in  dilute  sul- 
phuric acid,  boiled  with  washed  animal  charcoal,  and 
allowed  to  cool.  A  second  crop  of  crystals  of  quinia 
sulphate  is  thus  obtained.  The  mother  liquor  contains 
cinchonia  sulphate.  This  sulphate  is  dissolved  in  30 
times  its  weight  of  boiling  water,  allowed  to  cool,  and 
a  slight  excess  of  ammonia  added. 

The  cinchonia  which  is  precipitated  is  collected  on 
a  filter,  and  washed  with  lukewarm  tvater  until  the 
filtrate  no  longer  gives  with  barium  chloride  a  white 
precipitate  insoluble  in  acids;  it  is  then  dried  at  a 
temperature  of  30°  to  40°. 

Quinia  is  white,  amorphous  and  very  friable.     It 


SULPHATES    OF    QUINIA.  153 

may  be  obtained  in  a  crystalline  condition,  by  adding 
an  excess  of  ammonia  to  a  dilute  solution  of  quinia 
sulphate,  and  allowing  the  solution  to  stand. 

This  crystallized  quinia  melts  at  57°,  losing  its  water 
of  crystallization,  solidifies  and  remelts  at  176°.  It 
requires  250  parts  of  boiling  and  460  parts  of  cold 
water  for  its  solution. 

It  dissolves  in  2  parts  of  boiling  absolute  alcohol,  2 
parts  of  chloroform  or  50  to  60  parts  of  ether.  Its 
solutions  are  very  bitter,  levogyrate,  and  for  the  most 
part  fluorescent. 

Heated  on  platinum  foil,  quinia  swells  up  and  in- 
flames, leaving  a  deposit  of  carbon.  Heated  with  po- 
tassa  it  produces  hydrogen  and  quinoleine;  (cinchon- 
lein);  it  also  furnishes  a  brown  compound  on  being 
triturated  with  iodine. 

Quinia  is  recognized  by  the  following  reactions.  It 
is  first  saturated  with  very  dilute  sulphuric  acid  and 
chlorine  water;  then  an  excess  of  ammonia  is  added, 
whereupon  a  green  color  is  obtained. 

On  adding  powdered  potassium  ferrocyanide  before 
the  aqua  ammonia  a  rose  coloration  is  produced,  which 
afterwards  becomes  dark  red. 

Quinia  has  a  basic  reaction;  it  forms  with  acids 
crystallizable  salts  from  which  the  alkalies  precipitate 
quinia.  It  is  a  base  which  saturates  two  molecules  of 
a  monobasic  acid. 

SULPHATES  OF  QUINIA.  Two  sulphates  of  quinia  are 
known;  that  obtained  by  the  process  we  have  above 


154  ORGANIC    CHEMISTRY. 

described,  is  the   neutral  sulphate,  though  generally 
known  as  the  basic  sulphate.     Its  formula  is 


This  salt  contains  74.3  per  cent,  of  quinia. 

It  crystallizes  in  very  delicate  needles  belonging  to 
the  clinorhombic  system,  and  which  effloresce  in  dry 
air.  It  dissolves  in  30  parts  of  boiling  and  740  parts 
of  cold  water;  also  in  60  parts  of  cold  absolute  alco- 
hol. It  is  very  nearly  insoluble  in  ether.  Its  solu- 
tions are  extremely  bitter.  It  becomes  phosphorescent 
on  being  heated,  and  subsequently  fuses. 

Heated  in  the  air  it  burns,  leaving  a  carbonaceous 
residue. 

On  adding  quinia  to  water  acidulated  with  sulphuric 
acid,  it  rapidly  dissolves  and  another  sulphate,  often 
called  the  acid  sulphate,  is  formed,  whose  formula  is 


It  is  on  account  of  the  difficult  solubility  of  the  pre- 
ceding salt,  and  the  great  solubility  of  this  latter  one, 
that  we  cautioned  against  the  employment  of  an  excess 
of  sulphuric  acid  in  the  preparation  of  quinia. 

This  salt  dissolves  in  11  parts  of  water  at  12°,  and 
in  9  parts  at  18°.  Sulphate  of  quinia,  heated  to  130° 
with  acidulated  water  for  several  hours,  is  transformed 
into  an  isomeric  dextrogyrate  base  called  quinicine, 
which  is  likewise  a  febrifuge. 

Medicinal  sulphate  of  quinia  always  contains  sulphate 


QUINIA.  155 

of  cinchonia,  and  its  presence  is  not  considered  fraudu- 
lent, even  when  it  contains  3.5  per  cent,  of  the  latter 
substance,  as  this  salt  is  necessarily  produced  in  the 
preparation  of  quinia.  Cinchonia  appears  to  be  of  little 
therapeutic  value,  and  is  often  added  to  sulphate  of 
quinia. 

This  adulterant  is  detected  by  weighing  out  0.5 
grams  of  the  salt,  and  adding  to  it  5  grams  of  ether. 
The  mixture  is  agitated  and  1.5  grams  of  concentrated 
ammonia  added.  If  no  cinchonia  is  present,  two  liquid 
layers  are  obtained  ;  if  it  is  present,  a  layer  of  this  al- 
kaloid is  formed  directly  above  the  ammonia.  Good 
commercial  sulphate  of  quinia  should  give  only  a  very 
thin  layer. 

The  amount  of  quinia  may  be  directly  determined 
by  decanting  and  evaporating  the  ethereal  solution, 
and  weighing  the  residue.  This  result  may  be  verified 
by  replacing  the  ether  in  another  determination,  by 
chloroform,  which  dissolves  both  bases;  the  residue 
obtained  by  the  evaporation  of  this  liquid  furnishes  the 
weight  of  the  quinia  and  cinchonia  together. 

Sulphate  of  quinia  sometimes  contains  sulphate  of 
quinidia;  this  base  is  precipitated,  together  with  cin- 
chonia, by  ether.  Its  presence  may  be  detected  by 
dissolving  one  gram  of  the  sulphate  in  30  grams  of 
boiling  water,  and  adding  to  the  solution  ammonium 
oxalate.  Oxalate  of  quinidia,  which  is  the  only  soluble 
oxalate  of  these  bases,  remains  in  solution,  and,  on  fil- 
tering, a  bitter  liquid  will  be  obtained,  in  which  the 
quinidia  may  be  precipitated  by  ammonia. 


156  ORGANIC    CHEMISTRY. 

In  case  sulphate  of  quinia  has  been  adulterated  with 
calcium  sulphate,  or  other  inorganic  substance,  it  may 
be  recognized  by  a  residue  which  will  be  obtained  on 
heating  the  sulphate  to  redness  on  platinum  foil. 

Sulphate  of  quinia  should  dissolve  in  80  per  cent. 
alcohol.  If  it  dissolves  in  water,  but  does  not  dissolve 
in  56  per  cent,  to  60  per  cent,  alcohol,  it  may  be  re- 
garded as  not  pure. 

If  adulterated  with  starch,  or  fatty  bodies,  a  clear 
solution  cannot  be  obtained,  even  in  very  large  quanti- 
ties of  water. 

Should  it  contain  sugar  it  will  emit  an  odor  of 
caramel  on  ignition,  and  blacken  in  contact  with  sul- 
phuric acid. 

Quinia  sulphate  to  which  salicin,  a  common  adulter- 
ant, has  been  added,  is  colored  red  by  sulphuric 
acid. 

Quinia  sulphate  is  chiefly  employed  in  cases  of  in- 
termittent fevers. 

CINCHONIA   OR    CINCHONINE. 


Cinchonia  was  discovered  by  Duncan  in  1803,  though 
first  recognized  as  an  organic  base  by  Pelletier  and 
Caventou  in  1820. 

It  differs  from  quinia  in  containing  one  atom  less  of 
oxygen  ;  it  has  never  been  converted  into  quinia. 

It  is  prepared  in  the  same  manner  as  quinia,  but 


CINCHONIA.  157 

from  the  Gray  Peruvian  Bark.  Cinchonia  separates 
out  in  crystals  on  the  evaporation  of  the  alcohol  with 
\vlnch  the  calcic  precipitate  is  washed. 

The  crystals  of  cinchonia  are  collected,  allowed  to 
drain,  and  the  liquid  which  runs  off  will  furnish  addi- 
tional crystals  on  being  evaporated.  To  this  mother 
liquor  sulphuric  acid  is  added  in  excess,  and  the  solu- 
tion slightly  evaporated. 

The  first  crystals  obtained  are  sulphate  of  quinia, 
which  is  less  soluble  than  sulphate  of  cinchonia. 
When  nothing  remains  but  a  very  concentrated  mother- 
liquor,  the  cinchonia  is  precipitated  by  ammonia,  and 
freed  from  quinia  by  washing  with  ether.  The  quinia 
dissolves,  while  the  cinchonia  remains  insoluble. 

The  latter  crystallizes  in  brilliant  colorless  crystals, 
which  are  insoluble  in  cold  water  and  ether,  soluble  in 
2,500  parts  of  boiling  water,  in  30  parts  of  boiling  90 
per  cent,  alcohol,  and  40  parts  of  chloroform. 

Its  solutions  are  very  bitter  and  dextrogyrate. 

Cinchonia  melts  at  about  257°;  on  heating  to  a 
slightly  higher  temperature  in  a  current  of  nitrogen, 
or  hydrogen,  it  is  completely  sublimed. 

With  chlorine  and  bromine,  it  furnishes  dichloride 
and  dibromide  of  cinchonia.  With  iodine,  a  yel- 
low crystalline  body  is  obtained,  whose  formula  is 


Heated  with  fused  potassa,  it  produces  quinoleine. 

Cinchonia  has  an  alkaline  reaction.  It  unites  with 
acids,  forming  salts  which  correspond  to  the  salts  of 
quinia,  though  generally  more  soluble. 


158  ORGANIC     CHEMISTRY. 

Cinchonia  sulphate,  heated  to  about  135°,  furnishes 
the  sulphate  of  an  isomeric  alkaloid,  cinchonicia  or 
cinchonicine. 

Cinchonia  is  employed  as  a  febrifuge  in  Holland,  and 
a  few  other  countries,  but  its  action  is  regarded  as  in- 
ferior to  that  of  quinia. 

QUINOIDINE. — Quinidia  is  a  base  obtained  from  the 
last  mother-liquor  in  the  preparation  of  quinia,  by 
precipitation  with  sodium  carbonate.  It  is  olten  min- 
gled with  another  alkaloid,  cinehonidia  or  cinchoni- 
dine,  and  it  is  this  mixture,  containing  chiefly  quinidia, 
which  is  called  quinoidine  in  commerce. 

Quinidia  is  isomeric  with  quinia ;  it  melts  at  160°. 
It  is  difficultly  soluble  in  water,  very  soluble  in  boil- 
ing alcohol,  and  slightly  soluble  in  ether.  Its  solutions 
are  dextrogyrate.  Quinidia  acts  as  a  febrifuge.  With 
chlorine  and  ammonia,  it  gives  the  same  reactions  as 
quinia,  and  forms  corresponding  salts. 

Quinoidine  contains,  as  we  have  said,  cinehonidia,  a 
substance  isomeric  with  cinchonia.  This  body  is  crys- 
talline, fusible  at  about  150°,  almost  insoluble  in  water, 
slightly  soluble  in  ether  and  chloroform  ;  boiling  alco- 
hol is  the  best  solvent  for  cinehonidia. 


STKYCHNJA.  159 


ALKALOIDS  OF  THE  STRYCHNOS. 

The  two  chief  alkaloids  are  strychnia  and  brucia. 
Desnoix  extracted  from  the  nux  vomica  another  alka- 
loid, which  he  named  igasuria  ;  but  according  to 
Schutzenberger,  this  body  is  a  mixture  of  several 
bases. 

These  alkaloids  are  extracted  from  the  fruit  of  the 
Strychnos  nux  vomica  ;  from  St.  Ignatius'  beans,  fruit 
of  the  Strychnos  Ignatii  ;  from  the  wood  of  Coulevre, 
root  of  the  Strychnos  colubrina  ;  from  the  upas,  the 
poison  of  indian  arrows,  extracted  from  the  Strychnos 
tieute>\  from  the  False  Angustura  Bark,  and  the  bark 
of  the  Strychnos  nux  vomica^  which  contains  princi- 
pally brucia. 

STRYCHNIA. 


vomica  is  pulverized  and  boiled  with  three  suc- 
cessive portions  of  water  containing  sulphuric  acid,  and 
these  decoctions  evaporated  in  a  water  bath.  When 
the  liquid  is  reduced  to  a  small  volume,  125  grams  ot 
quicklime  slacked  to  a  thin  paste  are  added  for  each 


160  ORGANIC     CHEMISTRY. 

kilo,  of  mix  vomica.  The  precipitate  is  collected  on  a 
doth,  washed,  dried,  and  treated  with  90  per  cent,  al- 
cohol. 

The  alcoholic  solution  is  distilled  to  three-fourths  its 
volume  and  left  to  crystallize.  The  crystals  obtained 
are  chiefly  strychnia  ;  these  are  allowed  to  drain,  then 
dissolved  in  water  containing  fa  its  weight  of  nitric 
acid,  and  the  solution  concentrated  in  a  water  bath. 

The  nitrate  of  brucia  remains  dissolved  and  the 
nitrate  of  strychnia  crystallizes  out.  These  crystals 
are  re-dissolved  in  water,  animal  charcoal  added,  the 
solution  brought  to  boiling  and  then  filtered. 

Ammonia  is  added  to  this  liquid,  the  precipitate 
washed,  dried,  and  dissolved  in  boiling  alcohol,  which 
deposits  the  alkaloids  on  cooling. 

This  method  is  at  present  very  advantageously  sup- 
planted by  the  process  given  for  the  production  of 
quinia,  which,  briefly  stated,  consists  in  treating  the  sub- 
stance with  lime  directly  and  employing  a  solvent  for 
the  alkaloids,  which  is  insoluble  in  water,  such  as  petro- 
leum or  amylic  alcohol. 

Strychnia  crystallizes  in  octahedrons  or  in  prisms  of 
the  rhombic  system;  they  are  colorless,  very  bitter,  and 
almost  insoluble  in  water  or  ether,  but  readily  soluble 
in  ordinary  alcohol  diluted  with  Y5  per  cent,  of  water. 
Strychnia  treated  with  potassa  furnishes  a  small  quan- 
tity of  quinoleine.  Iodide  of  ethyl  produces  with  this 
base  the  compound 


BEUCIA  161 

CaH22(02H5)NAI. 

Chlorine  gas  renders  even  a  dilute  solution  of  this 
alkaloid  turbid  and  the  liquid  becomes  acid;  this 
reaction  is  characteristic.  Bromine  also  forms  deri- 
vatives by  substitution.  Iodine  combines  directly  with 
the  molecule  of  strychnia. 

Strychnia  dissolves  in  strong  sulphuric  acid;  the  so- 
lution is  colorless  and  becomes  dark  blue  in  contact 
with  potassium  bichromate  or  lead  dioxide.  The 
color  rapidly  passes  to  red  and  finally  to  a  yellow. 

Strychnia  is  colored  yellow  by  hydrogen  nitrate 
only  when  it  contains  brucia,  a  trace  of  which  is  suf- 
ficient to  produce  the  change. 

Strychnia  forms  with  acids  cry  stall  izable  salts. 
The  nitrate  CoJI^lS^C^HNOg  crystallizes  in  fine 
needles  very  soluble  in  hot  water. 

Strychnia  is  among  the  most  powerful  poisons,  2  to 
3  centigrams  being  sufficient  to  cause  death.  There  is 
believed  to  be  no  reliable  antidote  for  strychnia  though 
F.  M.  Peirce  claims  that  small  doses  of  prussic  acid 
are  efficient  for  the  purpose.  (M-'  68-335.) 

BEUCIA. 


To  obtain  this  alkaloid  the  alcoholic  liquids  from 
which  strychnia  has  been  removed,  are  saturated  with 
oxalic  acid  and  evaporated.  The  crystals  of  oxal- 
ate  of  brucia  which  are  formed,  are  washed  with  95  per 


162  ORGANIC     CHEMISTRY. 

cent,  alcohol  and  redissolved  in  water.  The  solution 
is  decomposed  by  lime,  the  precipitate  collected,  dried 
and  dissolved  in  boiling  alcohol;  brucia  then  crystal- 
lizes out  and  is  purified  by  two  recrystallizations. 

Crystals  of  brucia  are  large  and  of  the  clinorhombic 
system;  they  are  soluble  in  alcohol,  insoluble  in  ether, 
but  soluble  in  850  parts  of  cold,  or  500  parts  of  boil- 
ing water. 

Concentrated  sulphuric  acid  strikes  a  rose  color  with 
brucia  which  afterwards  changes  to  green.  ^Nitric  acid 
colors  it  red,  and  if  heated  it  gives  off  nitrous  ether, 
methyl  alcohol  and  carbon  dioxide. 

Brucia  is  much  less  poisonous  than  strychnia. 

It  may  be  distinguished  from  strychnia  by  its  reac- 
tion with  nitric  acid.  A  red  color  is  produced  by 
brucia,  which  passes  to  violet  on  the  addition  of 
stannous  chloride.  This  latter  coloration  does 
not  take  place  with  morphia.  Brucia  is  also  one  of  the 
best  reagents  for  nitric  acid. 

CURAKINA. — From  the  arrows  of  the  Indians  living 
on  the  shores  of  the  Amazon  and  Orinoco,  a  brown 
resinous  matter  is  collected,  from  which  crystals  of  a 
substance  have  been  obtained  whose  poisonous  action 
is  exceedingly  rapid.  Preyer,  to  whom  we  owe  this 
discovery,  regards  its  formula  as  C10I115N,  and  has 
named  it  curarina. 

The  Indians  of  Dutch  Guiana  poison  their  arrows 
with  two  other  substances  no  less  dangerous:  urari 
and  tikunas.  These  three  substances  paralyze  the  ac- 
tion of  the  muscles  by  destroying  the  motor  nerves 


VERATKIA.  163 

(Claude  Bernard).  It  appears  that  urari,  though  a  fa- 
tal poison  when  introduced  into  the  blood  by  a  wound, 
may  yet  be  swallowed  with  impunity. 

DKASTIO   POISONS. 

"We  shall  not  describe  the  preparation  of  the  follow- 
ing alkaloids,  on  account  of  their  minor  importance. 
The  process  in  general  is  similar  to  that  by  which  the 
preceding  ones  are  prepared:  The  alkaloid  is  dissolved 
in  an  inorganic  acid,  precipitated  by  a  base,  and  redis- 
solved  in  an  appropriate  solvent. 

The  roots  of  the  white  hellebore  ( Yeratrum  album) 
and  its  seeds,  furnish  an  alkaloid  called  veratria, 
CgoHso^Og.  It  crystallizes  in  prisms  having  a  rhom- 
bic base.  They  are  very  bitter,  insoluble  in  water, 
soluble  in  alcohol  and  ether,  and  melt  at  115°.  Yera- 
tria  is  dissolved  by  strong  nitric  acid,  the  solution  be- 
ing violet.  Sulphuric  acid  colors  it  first  yellow,  then 
red. 

Three  other  poisonous  bases,  sabadillia,  colchinia, 
and  jervia,  are  found  associated  with  veratria  in  the 
Veratrum  album.  Jervia,  C.2oH,6E"2O32H2O,  (Ger- 
hardt  and  Wills'  analysis)  is  white,  crystalline  and 
fusible. 

These  bodies  are  very  corrosive  poisons,  producing 
great  irritation  of  the  alimentary  canal. 

ALKALOIDS   OF   THE    POISONOUS    SOLANACE^. 

The  belladona,  Atropa  belladona,  and  the  thorn- 
apple,  Datura  stramonium,  furnish  each  an  alkaloid 


164  ORGANIC     CHEMISTRY. 

called,  respectively,  atropia  and  daturia,  the  formula 
of  which  is  Cnll^C^. 

This  substance  crystallizes  in  fine  needles,  which  are 
fusible  at  about  90°,  and  are  partially  sublimed  at 
about  135°.  It  is  difficultly  soluble  in  water,  but  very 
soluble  in  alcohol  and  ether. 

Heated  with  an  oxydizing  agent,  such  as  potassium 
bichromate,  or  sulphuric  acid,  it  disengages  essence  of 
bitter  almonds,  easily  recognizable  by  its  odor,  and 
crystals  of  benzoic  acid  are  sublimed.  With  sulphuric 
acid  a  violet  color  is  produced,  accompanied  by  a  fra- 
grant odor  resembling  that  of  a  rose. 

Hydrochloric  acid  furnishes  two  acids  with  atropia, 
tropic  C9H10O3,  and  atropic  C9TI8O2. 

Cases  of  poisoning  by  atropia  are  rare,  but  instances 
in  which  persons  are  poisoned  by  the  berries  of  bella- 
dona  are  of  frequent  occurrence. 

The  black  henbane,  Hyosciamus  niger,  furnishes 
silky  needles  of  a  substance,  hyosciamine,  which  has 
much  resemblance  to  atropia,  but  whose  action  as  a 
poison  appears  to  be  less  violent. 

Its  physiological  action  is  on  the  nerves  rather  than 
on  the  muscles.  It  causes  less  dilation  of  the  pupil  of 
the  eye,  and  produces  a  sombre  delirium. 

Belladona  and  atropia,  the  datura,  the  henbane  and 
hyosciamine,  as  well  as  the  poisonous  solanaceae  in 
general,  should  be  classed  among  the  narcotic  poisons. 

Poisoning  produced  by  belladona,  and  by  most  of 
the  poisonous  solanacese,  is  characterized  by  great  dila- 
tion of  the  pupils  of  the  eyes.  The  patient  is  also 


ACONITINA.  165 

seized  with  vertigo  and  strange  hallucinations  followed 
by  a  turbulent  delirium  and  convulsions.  The  face  is 
congested,  respiration  difficult,  and  the  skin  often 
breaks  out  in  an  eruption  similar  to  that  in  rubeola 
(measles). 

No  antidote  is  known  for  these  poisons;  an  infusion 
of  unroasted  coffee,  tea,  or  other  astringent  substances 
is  recommended,  but  the  use  of  energetic  emetics  and 
purgatives  is  the  most  effic'ent  method  of  treatment. 

The  chemical  characters  of  these  alkaloids  has  not 
been  as  jet  very  fully  studied. 

Desfosse  has  extracted  from  the  woody  nightshade, 
Solanum  dulcamara,  from  the  berries  of  the  felon- 
wort  and  from  the  young  sprouts  of  the  potato,  Sola- 
numtuberosum,  a  substance  called  solanine,  043HT1NO16, 
a  highly  poisonous  alkaloid.  On  being  boiled  with 
acids,  it  furnishes  a  stronger  base  solanidine  and 
glucose. 

ACONITINA. 

Aconitina  is  extracted  from  the  monk's-hood, 
Aconitum  napellus,  as  a  colorless  amorphous,  bitter 
powder,  soluble  in  alcohol,  slightly  soluble  in  ether,  and 
almost  insoluble  in  water.  It  fuses  at  120°,  and  is  al- 
kaline. It  is  a  very  active  poison.  Planta  gives  its 
formula  as  O30H47]NT  O7  ( '*). 

Duquesnel  has  extracted  from  the  Aconitum  napel- 
lus  a  crystalline  alkaloid,  whose  formula  is 


166  ORGANIC     CHEMISTRY. 

DIGITALIN. 

This  substance  was  long  ago  obtained  in  an  amor- 
phous condition  from  the  purple  fox-glove.  In  1871 
]NTativelle  succeeded  in  obtaining  it  in  a  crystalline 
form.  An  extract  of  fox-glove  is  first  prepared,  con- 
centrated by  distillation  and  dilluted  with  3  times  its 
volume  of  water. 

A  precipitate  is  formed  which  contains  two  bodies, 
digitalin  and  digitin.  This  deposit,  washed  with 
boiling  alcohol,  furnishes  crystals  composed  of  these 
two  substances,  which  are  easily  separated  by  chloro- 
form, as  digitalin  is  dissolved  by  it  in  all  proportions, 
while  digitin  is  insoluble. 

The  proportion  of  digitalin  in  Digitalis  grown  in 
different  countries,  has  been  made  the  subject  of 
special  investigation  by  Prof.  S.  P.  Duffield,  of 
Detroit.  (94-1868.) 

Digitalin  is  very  bitter  to  the  taste.  It  powerfully 
irritates  the  nostrils,  and  is  an  active  poison.  If  digi- 
talin be  moistened  with  strong  sulphuric  acid  and  then 
exposed  to  the  vapors  of  bromine,  it  assumes  a  purple 
color,  which  is  darker  or  lighter  according  to  the  pro- 
portions employed.  Hydrochloric  acid  produces  with 
digitalin  a  very  intense  emerald  green  color. 

One-fourth  of  a  milligram  is  sufficient  to  produce 
the  ordinary  poisonous  effects  oi  digitalis.  A  milli- 
gram produces,  in  from  three  to  five  days,  a  marked 
change  in  the  circulation.  Three  milligrams  produce 
most  dangerous  effects  within  24  hours. 


EMETIA.  167 

It  is  much  to  be  desired  that  physicians  substitute 
this  crystalline  substance,  which  is  invariable,  for  the 
amorphous  digitalin,  which  varies  greatly,  both  as  to 
character  and  effectiveness.  Tardieu  places  digitalin 
among  the  hyposthenic  poisons. 

Poisoning  by  digitalin  has  often  been  produced 
through  imprudence. 

The  "ipas  antior,  with  which  the  Indians  poison 
their  arrows,  is  obtained  from  the  Antiaris  toxicaria. 

EMETIA. 

This  body  is  obtained  from  the  roots  of  the  ipecac- 
uanha, Cephceles  ipecacuanha;  it  also  exists  in  the 
Richardsonia  braziliensis,  in  the  Phsychtria  emetica, 
and  in  the  roots  of  the  Cainca  (madder  tribe).  These 
materials,  reduced  to  a  powder,  are  treated  with  con- 
centrated alcohol,  and  the  alcohol  then  distilled  off. 
The  extract  is  diluted  with  five  times  its  volume  of 
water,  and  filtered.  To  the  filtrate  2  per  cent,  of 
caustic  potassa  is  added,  and  this  mixture  agitated 
with  chloroform.  The  chloroform  is  decanted  and 
distilled  ;  the  emetia  crystallizes  out.  It  is  dissolved 
in  dilute  sulphuric  acid,  and  precipitated  from  the  so- 
lution with  ammonia.  A.  Glenward  (105-[3]  6 — 201) 
gives  C^H^CXi  as  the  formula  of  emetia. 

It  is  amorphous,  yellowish,  fusible  at  50°,  soluble 
in  water  and  alcohol.  Its  solutions  are  slightly  bitter. 
It  is  a  very  weak  base,  and  its  salts  are  not  crystalline. 
A  few  centigrams  suffice  to  produce  vomiting. 


168  ORGANIC     CHEMISTRY. 

CANTHAKIDIN 

is  a  very  poisonous  crystalline  substance,  obtained  from 
Spanish  flies,  (Lytta  vesicatoria,  and  other  varieties) 
and  has  the  composition  C5H6O2.  It  is  present  in 
nearly  all  parts  of  the  flies,  varying  in  amount  from  0.5 
to  1.2  per  cent.  K.  Wolff  has  of  late  given  this  sub- 
stance a  very  full  investigation.  (95,  May,  '77-102.) 

CAFFEINE  (CAFFEIA)  OR  THEINE  (THEIA). 
C8H10N402,H20. 

Alcohol  is  added  to  a  mixture  of  5  parts  coffee  and 
1  part  slacked  lime,  until  nothing  further  is  dissolved, 
and  the  solution  distilled.  The  residue  is  treated 
with  water,  which  causes  an  oil  to  separate  out 
The  watery  liquid  fnrnishes  crystals  which  are  puri- 
fied by  treating  with  animal  charcoal,  and  recrystal- 
lizing  in  hot  water. 

The  extractive  matters  of  the  Jcola-nut  sndmate  pos- 
sess the  same  properties  as  caffeine. 

Caffeine  crystallizes  in  flue  needles,  fusible  at  178°, 
and  is  volatile  at  a  slightly  higher  temperature.  These 
crystals  are  but  little  soluble  in  ether  and  cold  water, 
yet  dissolve  very  readily  in  alcohol  and  boiling  water. 

It  is  remarkable  that  the  instinct  of  man  should 
have  led  him  to  select,  as  the  bases  of  common  bever- 
ages, just  the  four  or  five  plants,  which  out  of  many 
thousands  are  the  only  ones,  as  far  as  we  know,  con- 
taining caffeine. 


THEOBEOMINE.  169 

It  is  recognized  by  boiling  with  fuming  nitric  acid;  a 
yellow  liquid  is  produced.  On  being  evaporated  to 
dry  ness,  and  ammonia  added  to  the  residue,  a  purple 
coloration  is  produced,  resembling  murexide.  (p.  125.) 
Amalic  acid  and  CholestropJian  are  products  of  the 
action  of  oxidizing  agents  upon  caffeine;  bodies  link- 
ing this  alkaloid  to  the  uric  acid  group. 

THEOBKOMINE. 

There  is  extracted  from  the  caco,  Theobroma  cacao,  a 
principle  crystallizing  in  microscopic  crystals,  volatile 
at  295°,  soluble  in  alcohol  and  ether,  and  slightly  so  in 
water.  It  furnishes  salts  which  are  decomposed  by 
water.  It  is  called  tlieobromine\  its  formula  is  C7H& 

NA. 

PICEOTOXIN. 

C5H602. 

From  the  Indian  berry,  Cocculus  Indicus,  there  is 
extracted  a  white  crystalline  matter  of  extreme  bitter- 
ness, called  picrotoxin,  (from  Tempos  bitter  ro^ixor.) 
This  body  is  neutral,  difficultly  soluble  in  water,  and 
easily  soluble  in  alcohol  and  ether;  its  solutions  are 
levogyrate. 

The  physiological  action  of  picrotoxin  is  analo- 
gous to  that  of  strychnia,  but  it  differs  from  it  in  that 
it  renders  the  action  of  the  heart  slower,  and  produces 
vomiting. 

Prof.  J.  W.  Langley,  of  Pittsburg,  has  contributed 


170  ORGANIC    CHEMISTRY. 

much  to    (87-1862)    our  knowledge  of  the  chemical 
character  of  pi  cro  toxin. 

POLYATOMIC    ALKALOIDS. 

There  are  polyatomic  bases  which  are  to  the  mona- 
tomic  bases  what  polyatomic  alcohols  are  to  monatomic 
alcohols. 

They  are  built  upon  the  type  of  several  molecules 
of  ammonia,  or  condensed  ammonia,  in  the  same  man- 
ner that  polyatomic  acids  and  alcohols  are  derived 
from  several  molecules  of  water. 

Cloez  obtained  the  former  by  the  action  of  ethylene 
bromide  upon  potassa  dissolved  in  alcohol. 

Hoffmann  established  their  true  formula.  They  are 
called  poly  amines. 

EXAMPLE. 

(  C2H/ 
Ethylenic  dianiine,  No  •<      H2 


(  O.TV 

Diethylenic      "       N2  \  C2H4" 
\     H2 

(  C.H/ 

Triethvlenic    "        N2  \  C2H4" 
I  C2H4" 

IJEEA. 


POLYATOMIC    ALKALOIDS  171 

JRouelle,  Jr.,  was  the  first  to  obtain  this  body  in  an 
impure  state  from  urine. 

Fourcroy  and  Yanquelin  first  obtained  it  pure. 

Woehler,  in  1828,  prepared  it  artificially  by  a  remark- 
able synthesis,  the  first  attempt  to  form  a  body  syn- 
thetically. Urea  forms  the  chief  constituent  of  the 
urine  of  mammalia,  amounting  to  nearly  one-half  of  the 
solid  constituent;  a  small  proportion  of  urea  is  found 
in  all  the  fluids  of  the  body. 

It  is  an  excretory  product,  as  the  hydrogen  and 
carbon  which  have  taken  their  part  in  the  body,  escape 
mainly  in  the  form  of  water  and  carbon  dioxide,  so 
the  nitrogen  is  eliminated  from  the  system  chiefly  in 
the  form  of  urea. 

Urea  may  be  extracted  from  urine  by  evaporating 
this  liquid  to  one-tenth  its  volume  and  adding,  after  it 
has  become  cold,  an  excess  of  nitric  acid.  Brown 
crystals  of  nitrate  of  urea  are  formed :  these  are  drain- 
ed, expressed,  re-dissolved  in  water  and  boiled  with 
animal  charcoal.  This  solution  is  filtered,  and  on 
evaporation  it  deposits  crystals  of  nitrate  of  urea. 
This  salt  is  then  dissolved  in  as  small  a  quantity  of 
water  as  possible,  and  the  solution  treated  first  with 
barium  carbonate,  then  with  a  strong  solution  of  potas- 
sium carbonate;  urea  is  set  free  and  barium  and  potas- 
sium nitrates  formed.  The  above  mentioned  salts  are 
added  as  long  as  effervescence  is  produced;  the  liquid 
is  then  evaporated  to  dryness,  and  the  residue  treated 
with  absolute  alcohol,  which  dissolves  only  the  urea. 
(J.  E.  Loughlin,  100-5-362.) 


172  ORGANIC     CHEMISTRY 

The  synthetic  method  employed  by  Woehler,  con- 
sists in  preparing  cyanate  of  ammonia,  which  body  is 
isomeric  with  urea. 

CYANATE  OF  AMMONiuM=H4CE"2O=NH4-O-C!N". 

This  substance  changes  spontaneously  into  urea. 

Heat,  upon  an  earthen  plate,  28  parts  of  potassium 
ferrocyanide  and  14  parts  of  manganese  dioxide,  both 
finely  pulverized,  and  dry  until  the  mixture  becomes 
pasty;  when  cold,  the  mass  is  pulverized  and  treated 
with  water,  and  20  parts  of  ammonium  sulphide  added 
to  the  liquid,  which  is  now  evaporated  in  a  water  bath, 
and  the  residue  treated  with  boiling  alcohol.  On 
evaporating  the  alcoholic  solution,  crystals  of  urea  are 
deposited.  Urea  is  also  obtained  as  a  product  of  other 
reactions.  It  crystallizes  in  prisms  of  the  tetragonal 
system;  these  crystals  are  colorless,  without  odor,  and 
have  a  cooling  taste. 

It  is  soluble  in  its  own  weight  of  water  at  15°,  in  an 
equal  weight  of  boiling  alcohol,  and  in  5  parts  of  cold 
80  per  cent,  alcohol;  it  is  difficultly  soluble  in  ether. 
Its  solutions  are  neutral. 

Urea  fuses  at  120°;  at  about  150°  it  is  decomrjosed, 
yielding  ammonium  carbonate,  ammelide,  C3OH5N5, 
and  fiiuret,  C2O2H3N3. 

Oxydizing  agents  decompose  urea.  Chlorine  also 
decomposes  solutions  of  urea  in  the  following  man- 
ner: 

3C12  +  H2O  +  CH4lSr2O-6HCl  -1-  JST2 + CO2 . 

Urea  heated  to  140°  with  water  in  sealed  tubes,  is 
transformed  into  ammonia  and  carbon  dioxide: 


UREA.  173 

H2O  +  CH4]$r20=C0 


This  transformation  likewise  occurs  when  urea  is 
heated  with  strong  sulphuric  acid,  or  fused  with  po- 
tassa,  also,  spontaneously,  in  presence  of  the  nitro- 
genous matters  of  the  urine. 

Urea  does  not  appear  to  unite  with  all  acids.  It  has 
not  yet  been  combined  with  carbonic,  chloric,  lactic  or 
uric  acids.  The  nitrate,  chloride  and  oxalate  of  urea 
are  crystalline. 

Urea  forms  combinations  with  mercury,  silver, 
and  sodium  oxides,  also  with  mercuric  and  silver 
nitrates,  etc. 


174  ORGANIC    CHEMISTRY. 


NATURAL  FATS  AND  OILS. 

The  fatty  bodies  are  very  widely  distributed  through- 
out the  vegetable  and  animal  kingdoms.  Some  are 
liquid,  others  are  more  or  less  solid.  Certain  oils  re- 
main liquid  exposed  to  the  air,  as  olive  oil;  others 
oxydize  and  thicken,  as  linseed  oil,  poppy  oil,  and 
nut  oils;  the  latter  are  called  siccative  oils,  and  are 
used  in  the  manufacture  of  varnishes,  printers'  ink, 
oil  cloth,  also  in  paints. 

Fats  and  oils  are  insoluble  in  water;  they  are  among 
the  very  few  bodies  which  are  wholly  insoluble  in 
this  menstrum;  they  are  also,  in  general,  difficultly 
soluble  in  alcohol.  They  generally  dissolve  in  ether, 
and  the  liquid  hydro-carbons.  Their  specific  gravity 
is  less  than  that  of  water. 

Heat  destroys  them ;  acrolein  is  usually  formed 
associated  with  other  products. 

Since  oil  and  water  repel  each  other,  many  other 
substances  may  be  protected  from  moisture  by  simply 
coating  them  with  oil.  Shoe-leather  may  be  rendered 
water-proof  and  iron  protected  from  rusting  by  greas- 
ing- Wood,  saturated  with  oil,  will  last  for  a  long 
time  when  buried  in  moist  ground. 

STEARIN  OR  STEARINE,  (from  Greap,  suet)  C^H^Ce, 
is  prepared  by  melting  suet  in  turpentine;  the  two 
other  proximate  principles  present,  are  precipitated, 


FATS    AND    OILS.  175 

while  the  stearin e  remains  in  solution.  It  is  separated 
from  the  liquid  by  water,  and  purified  by  several  re- 
crystallizations  in  ether  ;  it  fuses  at  Tl°,  and  solidifies 
at' 50°. 

Berth elot  has  reproduced  stearine  synthetically,  by 
heating  3  parts  of  stearic  acid  with  one  part  of  glyc- 
erine, in  a  sealed  tube. 

This  synthesis,  as  well  as  other  researches,  estab- 
lishes the  fact  that  the  neutral  fats  are  compound 
ethers  of  glyceryl,  and  the  fatty  acids. 

On  account  of  the  heat  generated  by  oxidizable 
oils  when  exposed  to  the  air,  frequent  instances  of 
spontaneous  combustion  occur  when  cotton  rags,  or 
waste  soaked  with  oil,  are  allowed  to  remain  in  a  heap. 

Fats,  especially  if  mixed  witli  nitrogenous  matter, 
become  acid,  rancid.  The  chemical  nature  of  this 
change  is  not  entirely  understood. 

OLEIN  OK  OLEINE,  is  the  chief  constituent  of  olive  oil 
and  fish  oil.  Berthelot  has  shown,  by  the  action  of 
oleic  acid  on  glycerine,  that  natural  oleine  is  a  mix- 
ture of  monoleine,  dioleine,  and  trioleine.  Oleine 
heated  with  a  small  quantity  of  mercury  nitrate,  or 
any  other  body  capable  of  furnishing  nitric  oxide,  be- 
comes solid,  owing  to  the  transformation  of  the  oleine 
into  an  isomeric  body,  elaidine.  Siccative  oils  contain, 
instead  of  oleine,  another  principle  called  elaine. 

Neutral  fatty  bodies  and  other  ethers  of  glycerine 
are  decomposed  by  alkaline  solutions ;  a  combination 
with  water  takes  place,  glycerine  and  fatty  acids  are 
formed.  We  may  take  as  an  example,  stearin. 


176  ORGANIC    CHEMISTRY. 

3KHO+C57H11006=3(KC18H3502)+C3H803. 

Alkalies,  therefore,  react  upon  the  ethers  of  glycerine 
in  the  same  manner  as  do  the  ethers  of  glycol  and 
ordinary  alcohol.  This  reaction  is  called  saponificd- 
tion,  and  soaps  are  salts  formed  by  stearic,  margaric, 
and  oleic  acids,  with  a  metal. 

SOAPS.      STEARINS  CANDLES. 

The  only  soluble  soaps  are  those  whose  base  is 
potassa  or  soda.  Soda  soaps,  those  ordinarily  in  use, 
are  hard,  while  potassa  soaps  are  soft.  On  adding  to 
an  aqueous  solution  of  soap  a  solution  of  a  metal,  a 
precipitate  is  formed  which  is  the  soap  of  the  metal 
employed  ;  thus  the  precipitate  which  common  water 
produces  in  soap  is  a  lime  soap. 

Ordinary  soap  is  made  by  boiling  fats  of  inferior 
quality  with  an  alkaline  solution.  When  the  oil  is 
completely  decomposed  the  soap  is  precipitated  by 
salt  water,  in  which  soap  is  insoluble. 

Stearine  candles  have  hitherto  been  made  by  saponi- 
fying suet  or  tallow  with  lime  in  the  presence  of  boiling 
water.  At  present  the  amount  of  lime  employed  in 
the  saponification  is  considerably  diminished  (amount- 
ing to  only  4  per  cent.)  by  operating  at  a  temperature 
of  150°. 

The  saponification  of  fats  of  inferior  quality  is  also 
effected  by  means  of  sulphuric  acid  instead  of  lime; 
this  acid  forms  with  the  fatty  acids,  double  or  conju- 


FATS    AND    OILS.  177 

gate  acids,  which  are  decomposed  by  water.  The  de- 
composition of  fats  into  their  constituents,  the  fatty 
acids  and  glycerine,  for  the  manufacture  of  candles,  is 
at  present  effected  on  a  large  scale  by  simply  heating 
the  fats  with  steam  under  pressure,  and  at  a  tempera- 
ture of  260°.  This  is  the  celebrated  process  of  the 
American  inventor,  Tilghman,  to  whom  the  wonder- 
ful "  sand  blast "  is  also  due. 

This  decomposition  of  fats  is  most  remarkable,  as, 
by  the  same  process,  only  at  a  lower  temperature, 
Berthelot  obtained  a  result  exactly  the  reverse,  caus- 
ing stearic  acid  and  glycerine  to  reform  stearine  by 
simple  direct  synthesis. 

STEARIO  ACID,  C^H^C^,  is  crystalline,  insoluble  in 
water,  soluble  in  alcohol  and  ether,  and  melts  at  70°. 
It  unites  with  the  bases ;  its  alkaline  salts  alone  are 
soluble. 

MARGARIC  OR  PALMITIC  ACID,  C^H^O^,  (from 
jtapyapov,  a  pearl,  owing  to  its  pearly  lustre)  is  crys- 
talline. It  melts  at  60°  and  forms  salts  with  the  metals. 

OLEIO  ACID,  Cjgli^Oa,  is  an  oil  becoming  colored  in 
the  air  and  converted  into  an  acid  called  elaidic  acid, 
which  is  fusible  at  44°,  in  contact  with  a  small  quantity 
of  hyponitric  acid. 

These  three  a?ids,  stearic,  margaric,  and  oleic,  are 
those  that,  with  glycerine,  constitute  most  of  the  natu- 
ral fats,  or  glyceryl  ethers. 

LEAD  PLASTER  is  essentially  a  lead-soap  compound 
of  plumbic  oleate. 


178  ORGANIC     CHEMISTRY. 

CKOTON  OIL. 

This  oil  is  extracted  from  the  seed  of  the  Croton 
tiglium  of  the  family  of  euphorbiacese. 

The  seeds  are  ground  and  expressed,  or  they  are 
treated  with  ether,  which  is  afterwards  driven  off  by 
distillation. 

This  oil  is  yellowish,  very  bitter,  and  possesses  a 
disagreeable  odor.  Alcohol  and  ether  dissolve  it.  It 
produces  blisters  whenever  it  comes  in  contact  with 
the  skin,  and  is  a  drastic  poison. 

Pelletier  and  Caventou  have  extracted  from  this  oil 
an  acid  body,  C4H6O2,  denominated  crotonic  acid. 

COD-LIVER  OIL. 

This  oil  is  extracted  from  the  liver  of  the  cod,  and 
several  other  species  of  the  genus  Gadus.  Two  pro- 
cesses are  employed  for  its  extraction  ;  either  the  oil 
is  obtained  by  putrefaction,  in  which  case  the  oil 
separates  out  naturally,  or  the  livers  are  cut  into  small 
pieces  and  heated  in  large  pans,  then  placed  in  cloth 
sacks  and  pressed.  It  is  of  a  brownish  color.  A  white 
oil  is  sometimes  sold,  which  has  been  bleached  by 
treatment  with  weak  lye  and  animal  charcoal.  The 
efficiency  of  this  latter  oil  is  much  less  than  that  of 
the  natural  oil. 

There  has  been  found  in  this  oil  3  to  4  thousandths 
of  iodine,  and  a  small  quantity  of  phosphorous  ;  and 
its  medical  qualities  are  thought  to  be  due  to  these 


WAX.  179 

two  substances,  but  it  is  probable  that  its  efficiency  is 
more  frequently  due  simply  to  its  fatty  character. 

BUTTEB. 

Ordinary  Butter.  Butter  contains  stearic,  mar- 
garic,  oleic,  and  butyric  acids,  and  several  other 
proximate  neutral  principles.  Its  density  is  0.82.  It 
dissolves  in  30  per  cent,  of  boiling  common  alcohol. 
The  odor  which  it  emits  on  becoming  rancid  is  due  to 
the  liberation  of  fatty  acids. 

"  Oleo-margarine"  is  artificial  butter,  consisting 
mainly  of  oleine  and  margarine  obtained  from  suet  or 
lard. 

SPERMACETI. 

This  substance  which  is  formed  in  peculiar  cavities 
in  the  head  of  the  sp-arm  whale,  arid  is  a  neutral 
fatty  body  sometimes  employed  in  pharmacy.  It  is 
an  ether,  which,  on  saponifies ti on,  produces  a  fatty  acid 
called  ethalic  acid,  and  a  monatornic  alcohol,  ethal. 

H20+C33H6A=C16H31OHO  +  C^O 


Spermaceti.          Ethalic  Acid.  E;hal. 

WAX. 


Yellow  bees- wax  is  obtained  by  submitting  honey- 
comb to  pressure,  then  fusing  the  same  under  boiling 
water.  It  is  bleached  by  being  cut  into  thin  cakes 
and  exposed  to  the  air  and  sunlight.  Thus  prepared 


180  ORGANIC     CHEMISTRY 

it  fuses  at  62°.     Mixed  with   3  per  cent,  of  oil   of 
sweet  almonds  it  forms  a  cerate,  used  in  pharmacy. 

On  being  treated  with  alcohol  it  separates  into  two 
proximate  principles:  one,  soluble  in  this  liquid,  is 
acid,  and  is  called  cerotic  acid,  having  the  formula 
OjjH^O;  the  other,  which  is  but  slightly  soluble,  is 
called  myricin.  The  latter  is  a  compound  ether, 
and  is  decomposed  by  bases  into  an  acid,  ethalic  acid, 
and  an  alcohol,  melissic  alcohol,  C^H^O. 

CASTOR  OIL. 

This  oil  is  extracted  from  the  Ricinus  communis,  a 
plant  of  the  family  of  Euphorbiaceae. 

The  castor-oil  beans  are  hulled,  pulverized,  and 
the  pasty  mass  obtained  subjected  to  strong  pressure. 
This  oil  is  slightly  yellow.  Its  density  is  0.926  at 
12°,  and  it  remains  liquid  at  a  temperature  of —18°. 
It  is  very  soluble  in  alcohol,  a  characteristic  which 
distinguishes  it  from  most  other  oils. 
'  This  oil  is  also  an  ether  of  glycerine;  the  acid  which 
it  contains  is  ricinoleic  acid,  CjgH^Os. 


SUGARS.  181 


SUGAES. 

The  general  name  of  sugars,  by  some  regarded  as 
polyatomic  alcohols,  is  given  to  bodies  which  are  capa- 
ble of  fermenting,  that  is,  of  decomposing  directly  or 
indirectly  into  different  products,  of  which  the  princi- 
pal ones  are  alcohol  and  carbon  dioxide.  Fermenta- 
tion requires  the  presence  of  certain  microscopic 
plants,  and,  according  to  Pasteur,  is  a  phenomenon 
correlative  with  the  vital  development  of  these 
organisms.  This,  however,  has  been  latterly  dis- 
proved by  Tyndall. 

Sugars  may  be  divided  into  three  classes.  In  the 
first  are  those  in  which  the  proportion  of  hydrogen 
is  more  than  sufficient  to  convert  the  whole  of  the  oxy- 
gen into  water.  It  contains  : 

Mannite,  C6H14O(;,  extracted  from  manna. 

Duleite  or  melampyrite^  C6H14O6,  found  in  Mada- 
gascar. 

Finite,  C6TI12O5,  extracted  from  a  Californian  pine 
tree. 

Quercite,  C6H12O5,  extracted  from  acorns. 

These  bodies  do  not  ferment  with  beer  yeast  alone; 
but  in  presence  of  certain  ferments  and  calcium  car- 
bonate they  furnish  alcohol,  carbon  dioxide,  and  hy- 
drogen. 

Sugars  of  the  second  and  third  class  contain  hydro- 
gen and  oxygen  in  the  proportions  to  form  water. 


182  ORGANIC    CHEMISTRY. 

The  second  class  includes  the  glucoses,  isomeric 
bodies,  whose  general  formula  is,  C6H12O6.  Among 
these  are: 

Ordinary  Glucose  or  grape  sugar. 

JLevulose,  associated  with  glucose  in  the  form  of 
inverted  sugar. 

Maltose,  obtained  from  malt. 

Galactose,  obtained  by  treating  sugar  of  milk,  or 
gums,  with  dilute  acids. 

Eacalin,  obtained  by  the  action  of  maltose  on  beer 
yeast. 

Sorbin  exists  in  the  berries  of  the  mountain  ash. 

Inosite  is  found  in  the  embryo  of  young  plants 
and  in  the  fluids  of  flesh. 

Lactose  or  Sugar  of  Milk.  The  glucoses  may  be 
divided  into  two  series.  The  first  includes  those  bodies 
(ordinary  glucose,  levulose)  which,  on  being  oxydized, 
form  saccharic  acid,  and  on  being  hydrogen ized  by 
means  of  sodium  amalgam,  produce  mannite.  The 
second  includes  those  substances  (galactose,  lactose) 
which,  on  oxydation  produce  mucic  acid,  and  on  hydro- 
genation  furnish  dulclte.  The  third  class  of  su- 
gars contains  bodies  whose  general  formula  is  C^H^On, 
and  are  called  saccharoses,  by  Berthelot.  It  contains, 
besides  cane  sugar,  three  bodies  called: 

Melitose,  an  exudation  of  certain  eucalypti. 

Trehalose  or  mycose^  extracted  from  the  Turkish 
manna  and  certain  mushrooms. 

Melezitose,  obtained  from  an  exudation  of  the  larch. 

The  sugars  of  the  first  two  classes  are  placed  by 
Berthelot  among  the  polyatomic  alcohols. 


MANNITE.  183 

MANNITE. 

C,HU0, 

This  body  exists  naturally  in  an  exudation  of  vari- 
ous species  of  ash  (Fraxinus  rotundifolia\  called 
manna,  of  which  it  forms  the  greater  portion.  It  is 
also  found  in  mushrooms,  algae,  the  sap  of  most  fruit 
trees,  onions,  asparagus,  celery,  etc.  It  may  be  pre- 
pared by  dissolving  manna  in  one-half  its  weight  of 
water,  to  which  a  small  quantity  of  egg  albumen  is 
added,  and  the  mixture  brought  to  boiling  and  filtered. 
On  cooling,  colored  crystals  are  deposited  which  are 
expressed  and  redissolved  in  hot  water.  This  solution 
is  mixed  with  animal  charcoal,  boiled  and  filtered  while 
hot.  The  liquid  deposits  crystals  on  cooling.  Man- 
nite  crystallizes  in  rhombic  prisms  and  has  a  sweet  taste. 
It  dissolves  in  seven  times  its  own  weight  of  cold  wa- 
ter, is  slightly  soluble  in  alcohol,  and  insoluble  in  ether. 
Its  solutions  are  optically  inactive. 

Mannite  fuses  at  about  165°;  at  about  200°  it  yields 
a  certain  quantity  of  a  substance  called  Mannitane, 
C6H12O5.  It  oxydizes  in  presence  of  platinum  black, 
furnishing  a  non-crystallizable  acid  called  mannitic 
acid.  Boiling  nitric  acid  converts  it  into  saccharic 
and  oxalic  acids. 

Mannite,  treated  with  a  small  quantity  of  nitric  acid, 
is  changed  into  a  bodv  insoluble  in  water,  called 

('C  H ")  )" 
nitro -mannite,  (^fr\  \    ( 06,    which  may  be  regarded 

as  a  compound  ether. 

Dulcite. — Dulcite  is  very  analogous  to  mannite,  but 
differs  from  it,  in  that  it  furnishes,  with  nitric  acid, 
mucic  acid. 


184  ORGANIC     CHEMISTRY. 


GLUCOSES. 


These  compounds  may  be  considered  as  representa- 
tive carbohydrates.  Ordinary  glucose  (from  y\vH.v$, 
sweet,)  or  grape  sugar,  is  a  crystalline  substance,  and  is 
found  in  honey,  figs,  and  various  other  fruits,  together 
with  another  insoluble  glucose.  It  has  been  found  in 
small  quantity  in  the  liver  and  in  most  of  the  fluids 
of  the  body.  It  is  obtained  by  the  decomposition  of 
salicine,  tannin,  and  other  substances,  which,  for  this 
reason,  have  been  named  glucosides. 

Vegetable  cellulose,  the  envelope  of  many  inverte- 
brates (chitin  and  tunicin)  and  the  glycogenous  princi- 
ple of  the  liver  furnish  glucose  on  treatment  with 
dilute  acids. 

It  is  manufactured  on  a  large  scale  by  the  action  of 
starch  upon  dilute  sulphuric  acid.  Water  containing 
four  to  eight  per  cent,  of  sulphuric  acid  is  placed  in 
vats  and  heated  to  boiling  by  means  of  superheated 
steam.  Before  the  water  boils,  starch  mixed  with 
water  is  added,  and  ebullition  maintained  as  long  as  a 
small  quantity  of  the  mixture  gives  a  blue  reaction 
with  iodine.  The  sulphuric  acid  is  not  changed  during 
this  transformation. 

It  is  then  saturated  with  chalk  and  the  liquid  allowed 
to  become  clear.  It  is  decolored  by  passing  through 


GLUCOSES.  185 

filters  containing  animal  charcoal  and  evaporated  to  a 
density  of  41°  Baume.  The  glucose  crystallizes  in 
compact  masses.  Often  the  liquid  is  evaporated  to 
only  3°  B.,  when  a  syrup  is  obtained  known  as  starch 
syrup.  Honey  treated  with  cold  concentrated  alcohol, 
also  furnishes  glucose.  The  crystals  of  glucose  are 
small,  opaque,  and  ill  defined. 

They  are  represented  by  the  formula  C6H12O6,2H2O, 
but  they  may  be  obtained  having  the  composition 
C6H12O6  by  precipitating  the  glucose  in  boiling  concen- 
trated alcohol.  The  water  may  also  be  driven  off  by 
heating  the  glucose  to  about  100°. 

Glucose  is  soluble  in  a  little  more  than  its  own 
weight  of  water.  Weak  alcohol  dissolves  it  readily. 
It  is  slightly  soluble  in  cold  concentrated  alcohol. 

Its  solutions  turn  the  plane  of  polarization  to  the 
right.  This  rotatory  power  is  feeble  in  the  cold. 

Glucose,  heated  to  about  170°,  acts  in  the  same  man- 
ner as  mannite.  Gelis  has  demonstrated  that  it  loses 
a  molecule  of  water;  the  body  formed  C6H10O5,  is 
called  glucosanc,  C6IL2O6= C6H10O5  +  H2O.  It  re- 
produces glucose  on  being  boiled  with  acidulated 
water.  If  glucose  is  boiled  with  dilute  nitric  acid, 
saccharic  and  oxalic  acids  are  formed.  Fuming  nitric 
acid  forms  with  glucose  a  very  explosive  compound. 

Hydrochloric  acid  turns  it  brown.  With  dilute  sul- 
phuric acid  it  furnishes  a  double  acid  (sulphoglucic 
acid}\  with  strong  sulphuric  acid,  carbon.  Glucose 
oxydized  with  care,  furnishes  saccharic  acid. 

Heated  to  100°  with  butyric,  or  various  other  acids, 


186  ORGANIC    CHEMISTRY. 

it  loses  water,  and  the  glucosane  formed  reacts  upon 
che  acid,  forming  an  ether,  saccharide,  or  dibutyric 
glucosane, 

(C6H6)         )Q 
(C4H70)H2  f  ^' 

This  body,  as  well  as  other  saccharides,  are  decom- 
posed under  the  action  of  boiling  acidulated  water, 
into  an  acid  and  glucose. 

Glucose  combines,  with  sodium  chloride,  forming 
several  crystalline  compounds;  it  also  forms  unstable 
compounds  with  the  metallic  bases, 

CaC6H1006 
BaC6HnO6,  etc. 

Peligot  has  shown  that  the  solutions  of  these  glucos- 
ates  are  gradually  changed  into  salts  of  a  special  acid 
» called  glucic  acid,  whose  formula  is 


Oupric  acetate  boiled  with  glucose  is  reduced  to  the 
state  of  suboxide. 

This  action,  which  is  very  slow  with  salts  of  copper 
with  inorganic  acids,  becomes  rapid  and  complete  in 
presence  of  alkalies.  On  adding  glucose  to  a  solution 
of  copper  sulphate,  this  salt  is  not  precipitated  by 
potassa.  If,  however,  the  liquid  is  heated,  it  deposits 
cuprous  oxide.  (Trommer's  test.)  This  reaction  is 
more  delicate  with  copper  salts,  whose  acids  are 


GALACTOSE.  187 

organic.  A  mixture  is  used  of  copper  sulphate, 
Rochelle  salt  and  soda  (Fehling),  or  a  solution  of 
copper  tartrate  in  potassa.  (Barreswil.) 

Prof.  "W".  S.  Hain^s  has  found  in  glycerine  a  very 
desirable  substitute  for  the  tartrate  in  Fehling' s  test. 
The  proportions  employed  by  him  for  qualitative  ex- 
aminations are:  cupric  sulphate,  30  grains;  potassic 
hydrate,  1^  drachms;  pure  glycerine,  2  fluid  drachms; 
distilled  water,  6  ounces. 

LEVTJLOSE,  C6H12O6. 

This  name  is  given  to  a  variety  of  glucose,  which  is 
found  in  many  fruits.  It  may  be  obtained  by  boil- 
ing inulin  with  water,  or,  better,  it  can  be  prepared 
from  cane  sugar  by  the  action  of  dilute  acids.  It 
differs  from  the  other  sugars  in  that  its  rotary  power 
diminishes  on  heating. 

GALACTOSE, 

C,HaO, 

This  body  is  produced  by  boiling,  for  two  or  three 
hours,  sugar  of  milk  with  water  acidulated  with 
sulphuric  acid.  It  is  soluble  in  water  and  insoluble  in 
alcohol;  nitric  acid  transforms  it  into-mucic  acid. 

INOSIN,  INOSITE  OK  MUSCLE  SUGAR. 

C6H12O6  +  2H2O. 
This  substance  is  found  in  many  animal  organs,  and 


188  ORGANIC     CHEMISTKY. 

is  the  chief  constituent  of  the  liquid  which  impreg- 
nates the  muscles. 

It  may  be  prepared  by  first  extracting  the  creatin 
from  the  muscles,  then  separating  the  inosic  acid  with 
baryta.  To  the  liquid  is  then  added  a  quantity  of 
sulphuric  acid  sufficient  to  precipitate  the  whole  of  the 
baryta  and  the  liquid  treated  with  ether,  which  dis- 
solves the  foreign  substances. 

The  aqueous  solution  is  removed  and  alcohol  added 
to  it  until  a  precipitate  is  formed.  Crystals  of  potas- 
sium sulphate  first  separate  out,  then  beautiful  crystals 
of  inosite.  This  substance  has  a  sweet  taste.  At  a 
temperature  of  100°  it  loses  two  molecules  of  water. 
It  dissolves  in  one-sixth  of  its  weight  of  water  while  it 
is  insoluble  in  ether  and  strong  alcohol. 

Inosite  is  without  action  upon  polarized  light.  It 
is  not  converted  into  glucose  by  the  action  of  dilute 
acids,  and  does  not  reduce  copper  salts.  Mixed  with 
milk  and  chalk  it  undergoes  lactic  fermentation. 
(Page  122.) 


SACCHAROSES  189 


SACCHAEOSES. 

ORDINARY  SUGAR, 


This  body  exists  in  a  large  number  of  plants, 
though  it  is  almost  exclusively  extracted  from  the 
sugar-cane  and  beet-root. 

The  sugar-cane,  Arunde  saccharifera,  contains  1Y 
to  20  per  cent,  of  sugar.  To  extract,  the  juice  of  the 
cane  is  first  obtained  by  expressing.  This  juice  repre- 
sents 60  to  65  per  cent,  of  the  total  weight  of  the  cane, 
and  would  alter  rapidly  in  the  air  if  care  were  not 
taken  to  bring  it  rapidly  to  a  temperature  of  70°,  and 
adding  a  quantity  of  lime.  The.  juice  soon  becomes 
covered  with  foam  and  deposits  different  albuminoid 
and  other  matters,  which  are  precipitated  by  the  lime. 
It  is  decanted  into  pans  and  rapidly  evaporated.  The 
sugar  crystallizes  out,  and  the  mother  liquor  is  evapo- 
rated as  long  as  it  furnishes  crystals.  The  thick  liquid 
which  remains  is  molasses.  The  sugar  thus  obtained 
is  brown  sugar,  and  is  subsequently  refined. 

The  beet-root  most  rich  in  sugar  is  that  of  Silesia. 
It  contains  about  10  per  cent,  of  sugar.  Sugar  crys- 
tallizes in  clinorhombic  prisms.  They  may  Be  readily 
obtained  by  slowly  evaporating  a  solution  of  sugar. 


190  ORGANIC    CHEMISTKY. 

The  crystals  of  ordinary  sugar  are  very  small,  as  the 
syrup  is  made  to  crystallize  quite  rapidly.  Cold  water 
dissolves  three  times  its  weight  of  sugar;  hot  water 
dissolves  it  in  all  proportions,  forming  a  syrupy  liquid. 
It  is  not  dissolved  by  cold  alcohol  or  ether.  Dilute 
alcohol  dissolves  it  in  proportion  as  it  is  more  or  less 
aqueous.  Its  solutions  are  dextrogyrate.  Sugar  melts 
at  about  180°,  and  yields  a  liquid  which  solidifies 
to  a  vitreous,  amorphous  mass,  called  barley  sugar, 
which  becomes  opaque  and  crystalline  after  some  time. 

If  sugar  is  heated  a  little  above  this  point,  it  is. 
transformed  into  glucose  and  levulosane. 

Ci2H22Oii— 06H12O6  +  C6H10O3. 

Levulosane. 

At  about  190°  sugar  loses  water,  becomes  browny 
and  finally  furnishes  a  substance  which  is  commonly 
known  as  caramel.  According  to  Gelis  three  pro- 
ducts of  dehydration  are  formed,  caramelane,  cara- 
melene  and  carameline.  At  a  temperature  of  230° 
to  250°  sugar  is  decomposed  into  carbon  monoxide, 
carbon  dioxide,  carbohydrides  and  different  empyreu- 
matic  products.  Sugar  is  transformed  slowly  in  the 
cold,  and  rapidly  at  80°,  in  contact  with  dilute  acids 
into  inverted  sugar,  which  is  thus  called  on  account 
of  its  inverted  action  upon  polarized  light.  On  pro- 
longed ebullition  the  solution  is  rendered  brown  and 
ulmic  products  are  formed.  Sugar  reacts  with  baryta 
water  and  lime  water,  forming  different  compounds 
called  sucrates  or  saccharates. 


SUGAR    OF    MILK.  191 

The  solutions  of  these  sucrates  are  decomposed  by 
carbon  dioxide  :  sugar  is  reformed.  Rousseau  makes 
use  of  this  fact  in  the  manufacture  of  sugar  on  a  very 
large  scale. 

Sugar  does  not  ferment  immediately  in  contact 
with  beer  yeast. 

SUGAR   OF    MILK,    LACTIN    OR    LACTOSE. 


It  is  obtained  from  mirk,  by  precipitating  the  casein 
with  a  few  drops  of  dilute  sulphuric  acid,  filtering 
and  evaporating  the  liquid. 

Crystals  are  deposited,  which  are  purified  by  re- 
dissolving  and  treating  with  animal  charcoal. 

In  Switzerland  large  quantities  of  sugar  of  milk 
are  made  by  evaporating  the  whey  which  remains 
after  the  separation  of  the  cheese. 

The  crystals  of  this  body  are  rhombic  prisms. 
This  sugar  is  insoluble  in  ether  and  alcohol,  and 
requires  2  parts  of  boiling  and  6  parts  of  cold  water 
for  its  solution. 

Its  solutions  are  dextrogyrate.  At  a  temperature 
of  about  140°  it  loses  H2O,  and  becomes  brown  at  160° 
to  180°. 

In  presence  of  sour  milk  and  chalk  it  undergoes 
lactic  fermentation. 

Sugar  has  been  found  in  a  sample  of  a  saccharine 
matter  extracted  from  the  sap  of  a  sapodilla  tree,  the 
tree  furnishing  caoutchouc. 


192  ORGANIC     CHEMISTRY 

Keichardt  lias  obtained  (60-475-807)  from  a  sugar 
distinct  from  ordinary  sugar,  a  body  though  having 
the  same  formula.  He  names  it para-arabin. 

HONEY. 

Honey  is  produced  by  the  domestic  bee  (Apis  mel- 
lifica),  an  insect  of  the  order  Hymenoptera. 

It  is  separated  from  the  wax  by  exposing  the  honey- 
comb to  the  sun,  on  wire  nets;  very  pure  honey  is 
thus  obtained. 

The  mass  which  remains  is  expressed,  and  this  prod- 
uct is  a  second  quality  of  honey,  more  colored  and 
of  a  less  agreeable  taste  and  odor  than  the  first.  The 
comb  is  then  heated  with  water  to  remove  the  remain- 
der of  the  honey.  The  wax  thus  isolated  is  melted 
and  run  into  moulds.  Honey  owes  its  sweet  taste  to 
several  sugars.  There  is  found  in  it  a  dextroyrgate, 
crystallizable  glucose,  and  on  removing  this  sugar 
there  remains  a  viscid  uncry stall izab]e  liquid,  which 
contains  levolose.  In  addition  to  these,  small  quan- 
tities of  ordinary  sugar  have  also  been  found  in 
honey. 

GLUCOSIDES. 

This  name  is  given  to  certain  bodies  which  have 
the  property  of  forming  various  products  by  combin- 
ing with  water,  among  which  is  glucose,  or  some  other 
saccharine  matter. 

This  change  is  produced  by  the  action  of  acids, 
bases,  or  by  the  action  of  ferments.  We  cite  the  fol- 
lowing, but  shall  only  study  the  most  important: 


GLTJCOSIDES.  193 

Salicin,  C13H18O7,  extracted  from  the  bark  of  the 
Willow. 

Amygdalin,  C^H^NOn,  extracted  from  the  Bitter 
Almond,  Amygdalus  communis. 

Orcin,  C7H8O2,  extracted  from  various  Lichens. 

Tannin,  C27H22O17,  extracted  from  the  Oak. 

Phlorizin,  C21H24O10,  extracted  from  the  Apple,  Pear, 
or  Cherry  tree. 

Populin,  C^H^Og,  extracted  from  Aspen  leaves. 

Arbutin,  C13H16O7,  extracted  from  the  leaves  of  the 
Uva-Ursa. 

Convolvulin,  C31H50O16,  extracted  from  the  Convol- 
vulus orizabensis  and  schiedeanus. 

Jalappin,  C^H^O^,  extracted  from  Convolvulus 
orizabensis  and  scammonia. 

Saponin,  a  white  amorphous  powder  whose  solution 
is  very  frothy  and  of  which  the  powder  is  very  sternu- 
tatory. 

Daphnin,  C31H32O17,  the  crystalline  matter  extracted 
from  the  bark  of  the  Ash  (Fraxinus  excelsior}. 

Cyclamin  C20H24O10,  extracted  from  the  tubercles  of 
the  Cyclamen  europceum. 

Quinovin,  C3oIi48O8,  a  resinous,  bitter  matter,  solu- 
ble in  alcohol,  existing  in  the  bark  of  the  Quina  nova 
and  other  cinchonas. 

Solanin,  C43H71NO16.  This  has  already  been  studied, 
(page  165). 

Esculin,  CsaH^ds,  extracted  from  the  bark  of  the 
Horse  Chestnut. 

Qnercitrin,  C29H30O17,  from  the  bark  of  the  yellow 
oak  (Quercus  tinctoria). 


194  ORGANIC    CHEMISTRY. 

Coniferin,  C16H;>2O8,  from  the  Larix  europaea,  etc. 
Vanillin,  from  the  Yanilla  bean,  and  recently  ob- 
tained artificially  (60-74-608). 

SALICIN,  Ci3H18O7  +  H2O. 

This  body  crystallizes  in  white  needles,  fusible  at 
120°,  insoluble  in  ether,  soluble  in  alcohol  and  water. 
These  solutions  are  levogyrate  and  very  bitter.  It  is 
used  as  a  febrifuge,  but  is  of  little  value  in  well  de- 
fined intermittent  fevers. 

It  has  as  a  distinguishing  chemical  character,  the 
property  of  becoming  red  with  sulphuric  acid. 

Tinder  the  action  of  dilute  sulphuric,  or  hydro, 
chloric  acid,  or  even  with  emulsin,  salicin  is  decom- 
posed. "With  the  latter  the  reaction  is: 

C13H1807  +  HaO=C6H1206  +  C7H  A 

Glucose.        Saligenin. 

In  contact  with  cold  nitric  acid  it  loses  hydrogen, 
and  a  body  is  formed  called  helicin,  C13H16O7. 

When  treated  with  oxydizing  agents,  it  gives  off  an 
odor  which  is  identical  with  that  of  the  essence  of 
meadow  sweet  (Spirea,  ulmaria). 

This  body  is  produced  especially  when  salicin  is 
treated  with  a  mixture  of  sulphuric  acid  and  potas- 
sium bichromate,  and  is  also  known  by  the  name  of 
hydride  ofsalicyl. 

Its  formula  is  identical  with  that  of  benzoic  acid, 
C7H16O2,  but  it  has  not  the  properties  of  this  acid. 


SALICIN.  195 

It  is  an  aromatic  liquid,  boiling  at  196°,  and  has  the 
property  of  oxydizing  spontaneously,  giving  rise  to 
an  acid  called  salicylic  acid,  C7H6O3. 

Salicin,  treated  with  fused  potassa,  furnishes  potas- 
sium oxalate  and  salicylate.  Cahours  has  shown  that 
essence  of  Gaultfieria  procumbens,  a  heath  of  New 
Jersey,  contains,  besides,  an  isomer  of  the  essence 
of  turpentine,  a  sweet-scented  liquid,  boiling  at  220°, 
which  is  salicylic  methyl  ether,  and  is  re-converted, 
in  contact  with  alkalies,  into  methyl  alcohol  and  sali- 
cylic acid  :  it  may  be  produced  artificially  by  treating 
wood  spirit  with  a  mixture  of  salicylic  and  sulphuric 
acids. 

Salicylic  or  oxybenzoic  acid  has  been  lately  pro- 
duced by  Kolbe  (56  -'74  -22),  by  a  remarkable  syn- 
thesis in  acting  on  carbolate  of  sodium  with  CO2. 

02=C6H60  +  C7 


Sodium  phenol.  Sodium  salicylate  of  sodium. 

It  has  now  come  to  be  a  very  important  article  in 
pharmacy  and  in  the  arts,  on  account  of  its  efficiency 
as  an  antiseptic,  equaling  or  surpassing  carbolic  acid 
(phenol),  yet  without  the  unpleasant  odor  of  the  latter 
body,  or  its  toxical  qualities.  As  of  considerable  im- 
portance theoretically,  it  should  be  stated  that  Herr- 
mann has  very  lately  (60- April,  '77)  obtained  salicylic 
acid  by  the  action  of  sodium  upon  succinic  ether. 


196  ORGANIC    CHEMISTRY. 


TANNINS. 

This  is  the  name  given  to  different  principles  exist- 
ing in  plants,  which  are  characterized  by  the  following 
properties: 

1st.  They  give,  with  ferric  salts,  a  black  coloration 
approaching  bine  or  green. 

2d.  They  precipitate  solutions  of  albuminoid  sub" 
stances,  particularly  those  of  gelatine. 

The  principal  ones  are: 

Tannin  of  oak,  C^H^On. 

"  cachou  (catechin  or  catechic  acid). 
"  quinquinia  (quinotannic  acid). 
"         "  coffee  (caffetannic  acid). 
"  fustic  (morintannic  acid). 

Oak  tannin  is  best  prepared  from  gall-nuts  which 
contain  much  more  than  does  the  bark.  The  nuts 
are  pulverized  and  submitted  to  the  action  of  commer- 
cial sulphuric  ether,  which  is  made  aqueous.  This 
ether  may  be  replaced  with  advantage  by  a  mixture  of 
600  grams  of  pure  ether,  30  grams  of  90  per  cent. 
alcohol,  and  10  grams  of  distilled  water  for  every 
100  grams  of  gall-nuts.  After  twenty-four  hours  the 
apparatus  contains  two  layers  of  liquid ;  the  upper  one 
is  ether,  containing  but  little  tannin,  while  the  lower 
one  is  a  very  strong  aqueous  solution  of  tannin. 

The  lower  layer  is  removed  and  evaporated  in  an 


TANNIN  197 

oven  on  shallow  plates.  There  remains  an  amorphous 
spongy  substance,  very  soluble  in  water,  less  soluble 
in  alcohol,  and  almost  insoluble  in  ether.  This  residue 
is  very  astringent  and  slightly  acid. 

Solutions  of  tannin  give  a  white  precipitate  with 
tartar  emetic. 

It  precipitates  solutions  of  the  alkaloids,  and  coagu- 
lates blood. 

With  solutions  of  gelatin  it  gives  a  voluminous  pre- 
cipitate, soluble  on  heating  in  an  excess  of  gelatin. 

Tannin  forms,  with  fresh  hide,  an  imputrescible  com- 
pound, which  is  leather.  The  art  of  tanning  is  based 
on  the  action  of  oak-bark  tannin  on  hides  from  which 
the  hair  has  been  removed,  usually  by  lime. 

G-ALLIO  ACID.  In  solution,  tannin  is  gradually  de- 
composed, the  liquid  becoming  covered  with  mould. 

Carbon  dioxide  is  disengaged  and  an  acid,  called 
gallic  acid,  is  formed. 

This  transformation  does  not  take  place  if  all  air  is 
excluded;  and  the  air  alone  is  not  sufficient.  It  requires 
the  presence  of  a  mycelium  of  a  mucedin  conveyed  to 
the  liquid  either  by  the  air  or  in  some  other  manner. 

This  transformation  is,  like  alcoholic  fermentation, 
a  phenomenon  correlative  with  the  development  and 
growth  of  an  organism.  On  boiling  tannin  with  water 
acidulated  with  hydrochloric  or  sulphuric  acid,  it  is 
decomposed  into  glucose  and  gallic  acid: 

C^AT + 4H2O=3(C7H605)  +  06H12O6- 

Gallic  acid.          Glucose. 


198  ORGANIC     CHEMISTRY. 

Gallic  acid  is  deposited  as  the  liquid  becomes  cool. 
It  is  purified  by  redissolvingand  treating  with  animal 
charcoal,  and  recrystallizing. 

O  TT  O  ) 

Gallic  acid,  C7H6O5=   fr  fr   f  Oft  crystallizes  in  silky 

needles,  soluble  in  three  parts  of  boiling  water,  but 
little  soluble  in  cold  water.  This  solution,  on  standing 
in  the  air,  becomes  altered  after  a  long  time,  carbon 
dioxide  is  disengaged  and  the  solution  turns  brown ; 
alkalies  accelerate  this  change. 

Gallic  acid  produces  a  blue  color  with  ferric  salts, 
and  precipitates  tartar  emetic,  but  does  not  precipitate 
gelatin  when  pure,  nor  the  alkaloids. 

Mixed  with  pumice-stone  and  heated  to  210°  it  pro- 
duces a  beautiful  sublimate  otpyrogallie  acid,  carbon 
dioxide  being  liberated  at  the  same  time. 

C7H605=C6H608+002. 

This  body  occurs  in  colorless,  acicular  crystals, 
fusible  at  about  115°,  and  soluble  in  2.5  parts  of 
water.  Its  solution  absorbs  oxygen  from  the  air,  in 
presence  of  alkalies,  and  becomes  quite  brown. 

It  reduces  gold  and  silver  salts,  and  forms  unstable 
compounds  with  certain  acids.  It  may  properly  be 
placed  among  the  phenols.  This  body  is  employed 
in  photography,  and  in  the  laboratory.  Mercadante 
(47-' 74-484)  finds  that  gallic  acid  is  injurious  to 
vegetation,  inasmuch  as  it  combines  with  the  mineral 
food  of  the  plant  rendering  it  insoluble. 

Grimaux  was  the  first  to  consider  gallic  acid  as 
tetratomic  and  monobasic  (77-620). 


VEGETABLE    CHEMISTKY.  199 


VEGETABLE  CHEMISTKY. 

At  the  moment  when  the  radicle  of  a  plant  appears 
nbove  the  ground,  its  vital  phenomena  undergo  a 
marked  change. 

The  plant  decomposes  carbon  dioxide,  water  and 
certain  nitrogenous  compounds  furnished  by  the  soil, 
and  grows  bj  retaining  carbon,  hydrogen,  nitrogen  and 
a  little  oxygen,  and  returns  to  the  air  the  greater  part 
of  the  oxygen  derived  from  the  carbon  dioxide,  water 
and  nitrogenous  compounds. 

Bonnet  observed,  in  the  last  century,  that  leaves, 
exposed  to  the  sun  in  areated  water,  disengage  a  gas, 
which  Priestly  showed  is  oxygen.  Sennebier  discovered 
that  this  oxygen  is  derived  from  carbon  dioxide.  De 
Saussure  verified  these  facts,  and  demonstrated  that 
this  decomposition  of  carbon  dioxide  does  not  take 
place  in  the  dark,  and  tluit  the  green  portions  of  the 
plant  alone  are  capable  of  effecting  the  change. 

J.  Belluci  (9-78-362)  has  lately  shown  that,  con- 
trary to  former  belief,  none  of  the  oxygen  exhaled  by 
plants  is  in  the  form  of  ozone. 

EXPERIMENT. — Place  a  few  leaves  in  a  flask  half  full 
of  water  containing  carbon  dioxide,  usoda  water,"  invert 
the  flask  over  a  glass  of  water,  and  expose  it  to  the  sun- 
light, after  having  covered  it,  if  the  sun  is  very  hot, 
with  a  sheet  of  transparent  paper;  minute  bubbles  will 


200  ORGANIC    CHEMISTRY. 

soon  be  seen  to  form  on  the  leaves,  as  small  as  the  point 
of  a  pin,  will  increase  in  size,  unite  and  mount  to  the 
upper  part  of  the  flask.  Transfer  this  gas  to  a  test- 
tube,  and,  on  examination,  it  will  be  found  to  be  oxy- 
gen. Substitute  for  this  flask  an  opaque  vessel,  or  per- 
form the  experiment  in  the  dark,  and  the  carbon  diox- 
ide will  not  be  altered  in  the  least. 

"Where  do  the  plants  find  this  carbon  dioxide  ? 
Chiefly  in  the  air.  Boussingault,  in  order  to  demon- 
strate this,  placed  under  a  bell-glass  some  peas  planted 
in  calcined  sand;  he  watered  them  with  pure  distilled 
water,  and  passed  air  into  the  glass;  the  peas  grew, 
flowered  and  bore  fruit. 

Now  the  substance  of  these  peas  contained  carbon 
hydrogen  and  nitrogen,  in  much  greater  quantity 
than  the  seed  from  which  they  grew,  consequently 
these  constituents  were  taken  from  the  air  and  water. 

If,  however,  the  air  be  made  to  pass  through  an 
alkaline  solution  before  escaping  from  the  vessel,  no 
carbon  dioxide  is  absorbed,  which  also  proves  that  the 
carbon  dioxide  existing  in  the  air  has  been  removed 
by  the  plant.  The  plant  takes  up,  in  the  same  man- 
ner, carbon  dioxide  from  the  water  which  passes  from 
the  soil  into  its  roots. 

Plants  are  also  capable  of  decomposing  water,  in 
fact,  Collin  and  W.  Edwards  have  proved  that  the  sub- 
merged stems  of  the  Polygonwn  tinctorium  and  cer- 
tain mushrooms,  exhale  hydrogen. 

On  the  other  hand,  Payen  has  proved  that  the  hy- 
drogen exceeds  the  oxygen  in  the  woody  parts  of 


VEGETABLE    CHEMISTRY.  201 

plants,  and,  indeed,  many  substances  produced  by 
plants,  as  oils  and  resins,  are  very  rich  in  hydrogen. 
In  short,  the  oxygen  contained  in  the  plant  would  not 
be  sufficient  to  oxydize  or  transform  into  water  the 
whole  of  the  hydrogen  it  contains,  consequently  it 
must  be  admitted  that  water  is  decomposed  by  plants. 
The  conditions  under  which  this  change  takes  place 
have  not  as  yet  been  determined. 

The  experiment  of  Boussingault  proves,  as  Ingen- 
housz  has  claimed,  that  the  air  furnishes  the  plant  with 
nitrogen ;  but  where  does  this  nitrogen  come  from?  Is 
it  taken  by  the  plant  from  the  free  nitrogen  of  the  atmos- 
phere? or  is  it  derived  from  the  nitric  or  nitrous  acids, 
or  from  the  ammonia  contained  in  the  atmosphere,  or, 
in  one  word,  from  the  nitrogenous  compounds  existing 
in  the  air? 

Boussinganlt  has  shown  that  while  certain  families 
of  plants,  principally  the  common  vegetables,  derive 
from  the  air  a  large  quantity  of  nitrogen,  even  taking 
up  free  nitrogen,  others,  the  cereals  for  instance,  derive 
nitrogen  chiefly  from  the  soil;  for,  on  causing  clover 
and  wheat  to  grow  in  calcined  sand  in  presence  of  air 
deprived  of  its  nitrogenous  compounds,  and  distilled 
water,  he  observed  that  the  clover  took  up  carbon,  hy- 
drogen, water  and  nitrogen,  while  it  appears  that  the 
wheat  obtained  from  the  air  carbon  and  wrater  only. 

Nitrogen,  which  is  present  in  the  air  in  the  form  of 
ammonium  nitrate,  is  absorbed  by  all  plants.  Direct 
experiments  have  shown  that  the  salts  of  ammonium, 
especially  ammonium  nitrate,  constitute  an  excellent 


202  ORGANIC     CHEMISTRY. 

compost,  and  consequently  this  nitrate  can  lose  its  oxy- 
gen, or  become  reduced  in  the  plant. 

Now,  it  is  known  that  urea  and  animal  excreta  are 
transformed  into  ammoniacal  compounds  on  exposure 
to  the  air ;  therefore,  in  order  to  obtain  a  good  crop, 
even  with  plants  which  take  up  the  nitrogen  of  the  air, 
it  is  necessary  to  employ  manures  which  furnish  not 
only  easily  assimilated  nitrogen,  but  those  which,  be- 
sides, furnish  the  plant  with  soluble  organic  com- 
pounds and  the  mineral  substances  necessary  for  its 
development  and  growth.  Of  these  latter  there  is  re- 
quired for  the  plant,  potassium  and  calcium  chlorides, 
sulphates,  phosphates,  etc. 

With  the  four  elements,  carbon,  hydrogen,  nitrogen, 
and  oxygen,  nature  forms  an  infinite  variety  of  com- 
pounds by  mysterious  methods,  to  which  we  have  not, 
as  yet,  the  key,  but  of  which  synthetical  research  gives 
us  some  idea.  Thus,  with  carbon  dioxide  and  water, 
Berthelot  produces  formic  acid;  with  formic  acid  he 
obtains  alcohol,  and  subsequently  acetic  acid.  Pasteur 
also  has  shown  that  glycerine,  one  of  the  principles  of 
fat,  is  produced  in  the  process  of  fermentation  and 
that  a  complex  acid,  succinic  acid,  is  also  formed  under 
the  same  circumstances.  However,  we  are  far  from 
knowing  how  to  produce  those  substances  which  nature 
forms  at  ordinary  temperatures,  and  with  only  four 
elements.  What  wondrous  chemistry  is  that  of  the 
plant,  fitted  by  an  all-wise  Creator  to  elaborate  with 
such  simple  materials,  the  beauteous  violet,  the  fragrant 
rose,  or  the  luscious  fruit ! 


VEGETABLE    CHEMISTRY  203 

By  combining  six  atoms  of  carbon  with  five  atoms 
of  water,  nature  forms  either  the  woody  principle,  cel- 
lulose, or  the  essential  constituent  of  the  potato,  starch. 
By  uniting  ten  atoms  of  carbon  with  sixteen  atoms  of 
hydrogen,  she  produces,  in  the  orange  and  in  the  pine, 
two  essences  or  oils  very  different  in  character.  By 
associating  the  four  organic  elements  she  forms  the 
most  different  substances,  the  nourishing  cereal  as  well 
as  the  most  deadly  strychnia;  and  often  products  as 
unlike  as  these  are  found  side  by  side  in  the  same 
plant. 

Thus  the  plant  is  a  structure  which  decomposes  car- 
bon dioxide,  water,  and  compounds  of  nitrogen;  which 
forms  its  substance  out  of  carbon,  hydrogen,  nitrogen, 
and  a  part  of  the  oxygen  of  these  compounds,  and 
which  exhales  oxygen.  Hence,  chemically,  it  would  be 
proper  to  call  the  plant  a  reducing  apparatus. 

We  should  add  that  the  flowers  and  portions  of 
plants  not  green,  also  the  buds  in  developing,  produce 
an  exhalation  of  carbon  dioxide,  and  that  during  ger- 
mination, and  especially  during  the  time  of  flowering, 
a  sensible  amount  of  heat  is  disengaged.  As  a  result 
of  this  elevation  of  temperature,  there  is  produced  in 
plants  some  slight  oxydation  or  combustion,  as  in  the 
respiration  of  animals. 

Hence,  we  must  conclude  that  plants  and  animals, 
in  many  circumstances  at  least,  deport  themselves  in 
a  similar  manner. 

Many  experimenters,  and  especially  Dutrochet  and 
Garreau,  go  further,  and  say  that  plants  and  animals 


204  ORGANIC     CHEMISTRY 

respire  in  an  identical  manner,  and  according  to  their 
theories  all  living  creatures  take  up  oxygen  and  exhale 
carbon  dioxide. 

The  experiments  of  Garreau  especially  deserve  at- 
tention. He  placed  branches,  detached  or  affixed  to 
the  plant,  in  vessels  full  of  air,  and  exposed  them  to  a 
diffused  light.  The  volume  of  the  air  was  known  and 
the  oxygen  absorbed  was  determined  by  a  special  con- 
trivance ;  the  carbon  dioxide  produced  was  removed 
by  placing  in  the  vessel  an  alkaline  solution  of  known 
weight.  Thus  the  variations  of  these  gases  were  care- 
fully studied. 

As  a  result  of  his  experiments  Garreau  claimed  to 
have  established  that  both  in  the  dark  and  in  the 
light,  there  is  an  absorption  of  oxygen  and  an  ex- 
halation of  carbon  dioxide,  but  the  amount  of  car- 
bon dioxide  collected  does  not  represent  the  amount 
really  exhaled,  as  the  greater  part  is  reduced  at  the 
moment  of  liberation.  From  these  facts  it  would 
appear  that  in  all  living  creatures  the  same  phenome- 
non of  respiration  takes  place,  which  consists  in  a 
consumption  of  oxygen  and  an  exhalation  of  carbon 
dioxide. 

This  phenomenon  is  associated  with  another  ;  viz., 
assimilation  or  nutrition.  It  is  here  that  the  differ- 
ence, indeed  a  complete  opposition,  between  the  two 
kingdoms  is  established.  The  plant  grows  by  re- 
ducing, under  the  influence  of  heat  and  sunlight, 
carbon  dioxide,  water  and  nitric  acid,  by  accumulating 
carbon,  hydrogen,  nitrogen  and  by  exhaling  the  greater 


OKGANIZED    SUBSTANCES.  205 

part  of  the  oxygen.  The  animal,  on  the  other  hand, 
forms  its  substance  from  that  of  the  plant,  oxydizing, 
or  consuming,  the  vegetable  products  with  the  oxy- 
gen of  the  air  exhaled  by  the  plants;  it  reduces  the 
complex  products  formed  in  the  vegetable  to  the  state 
of  carbon  dioxide,  water  and  ammonia;  thus  the  ani- 
mals supply  the  plants  with  food,  receiving  in  turn 
nourishment  from  them.  Those  desirous  of  further 
studying  this  and  other  interesting  topics  relating  to 
Vegetable  Chemistry,  will  find  very  valuable  the 
works  of  Prof.  S.  "W.  Johnson,  "  How  Crops  Grow," 
and  "How  Crops  Feed";  also  Prof.  John  C.  Draper's 
article  in  Am.  Jour.  Sci.  and  Arts,  'Nov.  1872,  entitled 
"Growth  of  Seedling  Plants." 

ORGANIZED    SUBSTANCES. 

Among  the  chemical  substances  of  which  we  have 
spoken  certain  ones  participate  more  in  vital  phe- 
nomena, and  have  more  definite  physical  structure  than 
do  others. 

These  are  designated  as  organized  or  organizable 
substances,  the  term  organic  being  reserved  for  the 
definite  compounds  studied  in  organic  chemistry.  All 
these  substances  play  an  important  part  in  the  veget- 
able kingdom,  forming  the  network  of  vegetable  tis- 
sue, as  cellulose  or  as  starch,  etc. 

CELLULOSE    OK    CELLULIN,    (C6H10O5)n. 

On  examining  a  young  plant  under  the  microscope, 


206  ORGANIC    CHEMISTRY. 

we  observe  that  it  is  built  up  of  little  cells  and  mi- 
nute, diaphanous  ducts  or  vessels  filled  with  sap  and 
air.  The  material  of  which  these  tissues  are  com- 
posed is  called  cellulose.  The  pith  of  the  elder,  cot- 
ton fibre,  and  paper  are  almost  exclusively  composed 
of  this  substance. 

Cellulose  is  a  carbo-hydrate ;  C6H10O5,  is  the 
formula,  ordinarily  given  to  it,  although  a  multiple 
formula  at  least  three  times  as  large,  or  C18H3oO15  is 
necessary  to  explain  certain  reactions  with  nitric  acid. 

EXPERIMENT.  Pure  cellulose  may  be  obtained  in  the 
following  manner :  cotton,  linen  or  paper  is  treated  with 
dilute  alkaline  solutions,  washed  and  immersed  in  weak 
chlorine  water;  finally  it  is  submitted  to  the  action  of 
various  solvents,  as  water,  alcohol,  ether  and  acetic 
acid  until  nothing  more  is  dissolved. 

This  substance  is  solid,  white  and  insoluble.  It  is 
destroyed  at  a  red  heat,  producing  carbon  and  numer- 
ous carbohydrides,  gaseous  and  liquid,  which  distil 
over.  With  monohydrated  sulphuric  acid  it  produces 
a  colorless,  viscid  liquid,  which  contains,  at  first,  an 
insoluble  substance  having  the  properties  of  starch  and 
yielding  a  blue  color  with  iodine.  If  the  action  of  the 
acid  is  continued,  the  whole  is  dissolved  and  the  same 
products  are  obtained  as  in  the  case  of  starch  when 
brought  in  contact  with  sulphuric  acid,  i.  e.  dextrin 
and  glucose.  To  separate  the  latter  substance,  it  is 
simply  necessary  to  saturate  the  acid  with  chalk  and 
evaporate  the  liquid. 

Concentrated  hydrochloric  acid  produces  the  same 


CELLULOSE.  207 

effect.  If  paper  be  immersed  for  an  instant  only  in 
sulphuric  acid,  diluted  with,  half  its  volume  of  water, 
and  carefully  washed,  it  acquires  the  toughness  of 
parchment.  Paper  thus  prepared  is  frequently 
employed  in  experiments  on  dialysis;  it  is  also  much 
used  by  pharmacists  to  cover  the  stoppers  of  bottles. 
It  is  known  in  commerce  as  vegetable  parchment. 

GUN  COTTON  OR  PYROXYLIN. 

Gun  cotton  was  first  made  by  Schoenbe-in,  in  1846. 

To  prepare  it  cotton  is  plunged  for  two  or  three 
minutes  into  fuming  nitric  acid,  or,  better,  into  a  mix- 
ture of  1  vol.  nitric  acid  (of  a  density  of  1.5),  and  2 
vols.  of  strong  sulphuric  acid;  it  is  then  thoroughly 
washed  and  dried  at  a  low  temperature. 

The  cotton  is  not  changed  in  appearance  other  than 
becoming  -somewhat  wrinkled.  When  well  prepared 
it  burns  completely,  leaving  no  residue.  The  tem- 
perature at  which  it  takes  fire  varies  from  100°  to  180° 
according  to  the  manner  in  which  it  has  been  pre- 
pared. It  is  cellulose  in  which  from  six  to  nine  atoms 
hydrogen  have  been  replaced  by  an  equivalent  quan- 
tity of  the  monad  radicle  NO2  that,  having  the 
formula  C]8H21O159]^O2,  has  the  greatest  explosive 
energy.  Pyroxylin  regenerates  cellulose  in  contact 
with  ferrous  chloride.  If  cellulose  be  considered  a  sort 
of  alcohol,  as  claimed  by  some,  pyroxylin  would  be  a 
nitric  ether  of  this  alcohol. 

Pyroxylin   has  the  advantage   over  gunpowder  of 


208  ORGANIC    CHEMISTRY. 

being  more  easily  prepared,  and  of  remaining  unaf- 
fected by  moisture,  but  its  cost  is  relatively  greater, 
and  its  shattering  power  renders  its  employment 
dangerous. 

The  term  collodion  (from  nok\a^  glue)  is  given  to  a 
preparation  obtained  by  dissolved  gun-cotton  in  a 
mixture  of  1  part  of  alcohol  and  4  parts  of  ether, 

Chas.  H.  Mitchell  has  made  (52-74-235)  a  number 
of  experiments,  with  the  view  of  ascertaining  the  rela- 
tive proportions  of  cotton  and  acid,  together  with  the 
proper  time  of  maceration  necessary  to  produce  a 
cotton  which  should  combine  the  largest  yield  with 
the  highest  explosive  power  and  solubility. 

The  following  formula  was  at  length  adopted: 

Raw  cotton,  .  2  parts. 

Potassium  carbonate,  1      " 

Distilled  water,  100      " 

Boil  for  several  hours,  adding  water  to  keep  up  the 
measure ;  then  wash  until  free  from  any  alkali,  and 
dry.  Then  take  of — 

Purified  cotton,  Y  oz.  av. 

Nitrous  acid  (nitric,  saturated  with  nitrous  acid), 
s.  g.  1.42,  4  pints. 

Sulphuric  acid,  s.  g.  1.84,  -     4      " 

Mix  the  acids  in  a  stone  jar  capable  of  holding  2  gals., 
and  when  cooled  to  about  80°  Fahr.,  immerse  the  cot- 
tori  in  small  portions  at  a  time ;  cover  the  jar  and 
allow  to  stand  4  days  in  a  moderately  cool  place  (temp. 
50°  to  Y00  Fahr.)  then  wash  the  cotton  in  small  por- 


CELLULOSE.  209 

tions,  in  hot  water,  to  remove  the  principal  part  of  the 
acid;  pack  in  a  conical  glass  percolator,  and  pour  on 
distilled  water  until  the  washings  are  not  affected  by 
solution  of  barium  chloride. 

Collodion,  on  spontaneously  evaporating,  forms  a 
transparent  and  impermeable  membraneous  coating, 
and  is  much  employed  in  photography,  also  somewhat 
in  surgery. 

Cellulose  is  attacked  by  chlorine;  the  use  of  solu- 
tions of  chloride  of  lime,  and  of  chlorine,  in  large 
quantities  in  washing,  or  bleaching,  will  cause  a  rapid 
deterioration  of  linen  or  cotton  goods. 

Schweizer  has  shown  that  cotton,  paper,  etc.,  is 
very  easily  dissolved  by  an  ammoniacal  solution  of 
copper.  Attempts  by  the  author  to  employ  this 
solution  for  a  '*  water-proof  "  coating  of  fabrics,  as  has 
been  suggested,  failed  to  yield  a  satisfactory  result,  on 
account  of  the  liability  of  the  coating  to  crack  and 
peel  off. 

Peligot  has  found  in  the  skin  of  silk  worms,  and 
Schmidt  has  discovered  in  the  envelopes  of  the 
Tunicates,  a  substance,  tunicine,  which  has  the  com- 
position and  properties  of  cellulose. 

Linen,  hemp,  cotton,  wood  and  paper  are  all  essen- 
tially cellulose. 


210  OEGANIC     CHEMISTRY. 


AMYLACEOUS  SUBSTANCES. 

These  substances  are  almost  universally  present  in 
plants;  particularly  that  known  as  starch  orfecula. 

The  potato  yields  about  20  per  cent,  of  starch.  In 
order  to  obtain  it,  this  root  is  grated  and  the  pulp 
placed  upon  sieves,  arranged  one  above  the  other,  and 
through  which  a  stream  of  water  flows. 

The  grains  of  starch  being  extremely  minute  pass 
through  the  meshes  of  the  sieve,  while  the  walls  of  the 
cells  remain  behind.  The  starch  is  washed,  drained, 
and  dried,  first  at  ordinary  temperature,  afterwards  by 
the  application  of  a  moderate  heat. 

STAECH.  a?(C6H10O5)  probably  C18H3oO15.  Flour 
contains,  besides  starch,  nitrogenous  substances,  de- 
nominated gluten;  this  gluten  is  capable  of  ferment- 
ing, whereupon  it  becomes  soluble,  while  the  starch 
remains  unaltered  and  insoluble.  Under  these  con- 
ditions the  gluten  gradually  dissolves,  disengaging 
ammoniacal  compounds,  hydrogen  sulphide  and  other 
products  of  putrefaction. 

At  the  end  of  twenty  or  thirty  days,  the  gluten 
having  become  dissolved,  the  liquid  is  removed,  and 
the  starch,  washed  and  dried,  shrinks  into  columnar 
fragments,  which  are  readily  pulverized  by  gentle 
pressure. 


STAKCH  211 

A  more  modern  method  is  that  employed  in  France, 
which  is  essentially  the  same  as  the  process  cited  above, 
as  that  used  in  making  potato  starch  here.  The  water 
carries  away  the  starch  while  the  gluten  remains  be- 
hind in  the  form  of  an  elastic  mass,  which  is  also  util- 
ized. For  this  purpose  it  is  incorporated  with  flour 
poor  in  gluten,  to  be  made  into  macaroni,  and  for  the 
manufacture  of  a  very  nutritive  preparation,  "  granu- 
lated gluten;"  it  is  also  employed,  according  to  the 
recommendation  of  Bouchardat,  in  making  bread  for 
persons  afflicted  with  diabetes. 

Starch,  examined  with  a  microscope,  exhibits  flat- 
tened ovate  granules  of  different  size  in  various  plants, 
but  always  very  small.  Those  of  the  Rohan  potato 
have  a  length  of  0.185  mm.;  the  smallest  are  those  of 
the  GJienopodium,  quinoa  whose  length  is  0.002  mm. 

"When  starch  is  heated  with  water  to  70°,  the  gran- 
ules increase  from  20  to  30  times  their  original  volume, 
and  become  converted  into  a  tenacious  paste.  A  small 
quantity  of  the  starch  passes  into  solution,  and  to  this 
the  name  amidin  has  been  given.  Starch  paste  and 
the  solutions  of  starch  have  the  characteristic  property 
of  becoming  blue  in  contact  with  small  quantities  of 
iodine.  The  liquid  becomes  colorless  at  about  70°,  but 
regains  its  color  on  cooling.  If  to  this  blue  liquid  a 
solution  of  a  salt,  sodium  sulphate  for  instance,  be 
added,  we  obtain  a  dark-blue  floculent  precipitate.  This 
substance,  called  starch  iodide,  is  not  a  chemical  com- 
pound, but  a  sort  of  lake,  containing  variable  quanti- 
ties of  iodine  diffused  throughout  the  starch  and  solv- 


212  ORGANIC    CHEMISTRY. 

ent.  This  reaction  with  iodine  is  a  very  valuable  test 
for  starch,  but  is  open  to  several  fallacies,  and  apt  to 
mislead  in  inexperienced  hands. 

Until  lately,  it  has  been  claimed  that  starch  is  insol- 
uble in  water,  and  that  if  water  in  which  starch  has 
been  boiled  gives  with  iodine  the  characteristic  reaction 
of  this  substance,  it  is  due  to  particles  of  starch  suffi- 
ciently minute  to  pass  through  the  pores  of  the  filter. 
But  the  results  of  the  experiments  of  Maschke  and 
Thenard,  show  that  if  starch  is  heated  for  some  time 
at  100°,  it  is  partially  transformed  into  a  variety  solu- 
ble in  water.  This  substance  is  colored  by  iodine;  it 
furnishes,  on  evaporation,  a  gummy  solid  which  is  pre- 
cipitated by  alcohol  as  an  amorphous  powder. 

If  we  boil  starch  for  a  long  time  with  water  it  is 
converted  into  a  substance  called  dextrin.  The  pres- 
ence of  a  small  per  centage  of  sulphuric  acid  facilitates 
this  change,  which  is  soon  followed  by  the  transforma- 
tion of  the  dextrin  into  glucose.  The  sulphuric  acid 
is  not  at  all  altered  during  the  reaction. 

The  change  ot  starch  into  glucose  also  takes  place 
when  water  containing  starch,  and  to  which  germinated 
barley  has  been  added,  is  heated  to  about  70°. 

This  transformation  is  due  to  a  substance  called 
diastase  (from  diaffraffis,  separation),  which  is  formed 
in  the  seed  during  germination.  The  production  of 
diastase  on  the  formation  of  the  young  shoot,  explains 
how  starch  becomes  soluble  and  serves  as  nutriment  to 
the  young  plant. 

Theptyalmof  the  saliva,  the  pancreatic  juice,  the 


STAKCH.  213 

soluble  parts  of  beer  yeast,  gluten,  and  many  other  sub- 
stances, are  capable  of  producing  this  transformation 
of  starch  into  dextrin  and  glucose. 

It  has  generally  been  considered  that  the  molecule 
of  starch,  in  being  transformed  into  glucose,  simply 
united  with  one  molecule  of  water  directly,  thus: 

C6H1005+H20=C6H1206. 

Musculus,  however,  claims  to  have  established  that 
the  starch  is  first  transformed  into  a  soluble  metamer, 
and  this,  thereupon,  splits  up  into  dextrin  and 
glucose; 

C18H3o015  +  H80=2C6H1005  +  C6H12O6. 

Dextrin.  Glucose. 

By  further  action,  the  whole  of  the  dextrine  becomes 
converted  into  glucose,  (2-[3]  60-203). 

Starch,  heated  simply  to  about  160°,  is  also  changed 
into  dextrin. 

It  is  attacked  by  dilute  nitric  acid,  nitrous  vapors 
are  given  oif  and  different  substances  are  produced, 
chiefly,  however,  oxalic  acid. 

If  starch  is  agitated  with  fuming  nitric  acid,  it  is 
dissolved  and  water  precipitates  from  the  solution  a 
nitrous  compound  which  is  explosive. 

The  alkalies,  in  concentrated  solutions,  when  heated 
with  starch  disorganize  and  dissolve  it.  Solutions  con- 
taining two  to  three  per  cent,  of  alkali,  accelerate  the 
formation  of  starch  paste. 


214  ORGANIC    CHEMISTRY. 

Starch  is  employed  in  the  laundry  and  therapeutic- 
ally  in  poultices,  injections  and  baths. 

Tagioca,  is  the  starch  of  the  root  of  the  Jatropa 
manihot,  called  cassava  or  manioc. 

Sago  is  obtained  from  the  pith  of  various  sago 
palms. 

Arrow-root  is  the  starch  of  the  Maranta  arundi- 
nacece*  and  one  or  two  other  tropical  plants. 

Salep  is  obtained  trom  the  Orchis  mascula. 

INULIN.  There  has  been  found  in  the  roots  of  the 
Jerusalem  artichoke,  of  the  chicory,  and  the  bulbs  of 
the  dahlia,  a  substance  isomeric  with  starch,  called 
inulin. 

LICHENIN.  There  is  extracted  from  certain  lichens 
and  mosses  a  substance  called  lichenin,  which  has  the 
property  of  swelling  in  cold  water  and  of  being  dis- 
solved in  boiling  water.  It  is  prepared  by  treating 
Iceland  moss  with  ether,  alcohol,  a  weak  solution  of 
potassa,  and  finally  with  dilute  hydrochloric  acid. 

There  exists  in  the  animal  organism  a  variety  of 
starch  designated  by  the  name  of  glycogen. 

DEXTKIN,  OR   DEXTRINE. 

C6H1005. 

To  prepare  dextrin,  starch  may  be  heated  with 
water  containing  a  small  quantity  of  sulphuric  or 
oxalic  acid  ;  the  operation  should  be  arrested  when 
the  liquid  gives  with  iodine  only  a  wine-colored  re- 
action. 


FLOUR  215 

For  the  acids,  a  small  quantity  of  germinated  bar- 
ley may  be  substituted,  placed  in  a  bag  immersed  in 
the  liquid.  Dextrin  thus  prepared  always  contains 
glucose.  It  may  be  obtained  free  from  this  substance 
by  heating  starch  with  -jr  its  weight  of  water  and  1 020  tf 
of  "nitric  acid. 

Dextrin  is  amorphous,  slightly  yellow,  very  soluble 
in  water,  insoluble  in  alcohol  and  concentrated  ether. 

It  is  used  somewhat  in  preparing  bandages  in  case 
of  fracture,  and  very  extensively  as  a  paste  for  calico- 
printers. 

Dextrin,  forms  viscid  adhesive  solutions  which  are 
used  for  the  same  purposes  as  gum-arabic.  The  mu- 
cilage used  by  the  U.  S.  government  for  postage 
stamps  is  composed  of  dextrin  two  ounces,  acetic 
acid  one  ounce,  water  five  ounces,  alcohol  one  ounce. 
Dextrin  may  be  distinguished  from  gum-arabic  by 
not  being  precipitated  on  adding  a  dilute  solution  of 
lead  acetate,  and  by  furnishing  with  nitric  acid  a  so- 
lution of  oxalic  acid  and  not  a  precipitate  of  mucic 
acid. 

FLOUK. 

Amylaceous  substances  are  of  great  importance  as 
food.  Wheat  and  other  cereals  are  the  most  import- 
ant .sources  of  these  aliments. 

Starch,  as  also  sugar  and  the  neutral  carbohydrates, 
are  respiratory  foods  whose  principal  eifect  is  the  pro- 
duction of  heat  by  being  oxidized,  or  burned,  in  the 
body. 


216  ORGANIC    CHEMISTRY. 

The  composition  of  four  of  the  leading  cereals  is- 
herewith  given : 


Ill     I    I!     9 


Wheat,  14.0 

59.5 

7 

1.7 

14 

1.2 

1.5 

Eye,      16.0 

57.5 

10 

3.0 

9 

2.0 

2.0 

Oats,     14.0 

53.5 

8 

4.0 

12 

5.5 

4.0 

Eice,      14.5 

77.0 

0.5 

7 

0.5 

0.7 

The  sticky,  elastic  substance  found  with  starch  in 
flour  is  gluten  (called  also  glutin),  and  is  a  mixture 
of  various  proximate  compounds  but  chiefly  of  three; 
legumin,  or  vegetable  casein,  fibrin  and  gelatine. 

Flour  of  good  quality  is  dry  and  soft  to  the  touch; 
it  forms  with  water  an  elastic,  non-adhesive  dough. 

The  value  of  flour  depends  largely  upon  the  gluten 
it  contains,  though  not  as  stated  in  most  authors  upon 
the  percentage  of  this  substance,  but  upon  the  quality 
rather,  as  shown  by  recent  investigations  of  R.  W. 
Kunis  (26-74-1487). 

The  modern  "patent  process,"  originating  in  Min- 
nesota, is  mainly  a  method  of  grinding  which  intro- 
duces into  the  flour  more  gluten  than  in  older  pro- 
cesses. 

GUM. 

C6H10O5. 

This  substance  is  very  widely  distributed  in  the 
vegetable  kingdom.  Gums  either  swell  in  water  or 


GUM.  217 

are  dissolved,  imparting  to  it  a  mucilaginous  consis- 
tency. 

From  a  chemical  standpoint  they  are  essentially 
characterized  by  giving  a  precipitate  of  mucic  acid 
on  being  boiled  with  nitric  acid,  and  by  precipitating 
lead  subacetate. 

GUM-ARABIC,  ARABIN.  This  gum  exudes  from  dif- 
ferent species  of  acacias,  as  Acacia  arabica,  A.  sene- 
galensis,  A.  vera  /  it  is  obtained  from  Arabia  and 
Senegal. 

According  to  Fremy,  gum-arabic  is  a  salt  formed 
by  the  combination  of  an  acid,  gummic  or  arable  acid, 
with  lime  and  potassa.  This  acid  may  be  isolated  by 
pouring  hydrochloric  acid  into  a  solution  of  gum,  and 
adding  alcohol;  an  amphorous  deposit  is  formed  which, 
dried  at  120°,  has  the  formula  C6H10O5.  This  acid  is 
very  soluble  in  water.  Its  solution  is  levogyrate,  like 
that  of  gum-arabic.  On  being  heated  to  150°  it  is 
transformed  into  a  substance  insoluble  in  water  called 
meta-gummic  acid,  whose  salts  are  likewise  insoluble. 
Gum-arabic  gives  with  ferric  salts  an  orange-colored, 
floculent  precipitate  soluble  in  acids. 

CEEASIN.  The  gum  which  exudes  from  cherry  and 
plum  trees  is  a  mixture  of  soluble  gummates  and  in- 
soluble meta-gummates ;  hence  it  is  only  partially 
soluble  in  water. 

Cerasin  becomes  soluble  on  being  boiled  with  water, 
as  the  meta-gummates  are  transformed  into  gummates 
by  the  action  of  boiling  water. 

These  gums  heated  with  dilute  sulphuric  acid  furnish 
a  dextrogyrate  sugar. 


218  ORGANIC    CHEMISTRY. 

Gum-tragacanth  often  contains  starch. 

MUCILAGE  OR  BASSOKIN.  There  exists  in  the  seeds 
of  the  quince  and  flax,  in  the  roots  of  the  marsh-mal- 
low and  in  portions  of  many  other  plants,  a  substance 
or  substances,  which,  exposed  to  the  action  of  boiling 
water,  furnhh  a  thick  mucilage,  which  appears  to  con- 
sist of  a  soluble,  together  with  an  insoluble  substance. 
Nitric  acid  converts  this  mucilage  into  mucic  and  ox- 
alic acids.  Gum  and  mucilage  are  frequently  em- 
ployed as  emollients,  and  in  syrups,  also  extensively 
in  confectionery. 

PECTIN  GROUP.  Many  roots,  as  the  carrot,  beet, 
etc.,  also  green  fruits,  contain  a  neutral  gelatinous 
substance,  insoluble  in  water,  alcohol  and  ether,  called 
pectose.  It  is  that  which  gives  to  green  fruits  their 
harshness.  This  substance  is  modified  during  the 
ripening  of  the  fruit  and  becomes  soluble,  vegetable 
jelly,  or  pectin  (from  Ttrjuri^^  a  jelly),  to  which 
Fremy  assigns  the  formula  CgjH^Oga. 

.Pectnij  submitted  to  the  action  of  a  ferment  found 
in  tli3  cellular  tissues  of  vegetables,  called  pectase,  or 
of  cold,  very  dilute,  alkaline  solutions,  is  changed  into 
a  gelatinous  acid  called  pectosio  acid,  then  into 
another  substance  likewise  gelatinous,  which  is  known 
by  the  name  of  pectic  acid.  All  these  substances  are 
amorphous,  and  non -nitrogenous.  Their  formulae  are 
not  yet  definitely  determined. 

According  to  Fremy,  to  whom  we  are  indebted  for 
the  foregoing  facts,  the  jelly  obtained  from  the  current 
and  other  fruits  is  due  to  the  action  of  the  pectase  on 
the  -oectin  of  these  fruits. 


LEGUMIN.  219 

These  substances  resemble  gums  in  producing,  on 
boiling  with  nitric  acid,  a  precipitate  of  mucic  acid. 

Much  doubt  still  exists  respecting  the  composition 
of  the  pectin  group. 

LEGUMIN  OR  VEGETABLE   CASEIN. 

Legumin  is  found  in  most  leguminous  seeds,  such 
as  sweet  and  bitter  almonds,  also  in  beans,  peas,  etc., 
the  latter  containing  about  25  per  cent.  It  is  con- 
sidered to  be  identical  with  casein  by  Liebig  and 
Woehler. 

It  may  be  obtained  by  digesting  coarsely  powdered 
peas  in  cold  or  tepid  water  for  two  hours,  allowing 
the  starch  and  fibrous  matter  to  subside,  and  then 
filtering  the  liquid.  It  forms  a  clear,  viscid  solution, 
which  is  not  coagulated  by  heat  unless  albumen  is  also 
present,  but,  like  emulsin  and  unlike  albumen,  it  is 
precipitated  by  acetic  acid.  It  is  coagulated  by  lactic 
acid,  also  by  alcohol;  in  the  latter  case  the  precipitate 
is  redissolved  by  water. 

Acetic  acid,  diluted  with  8  to  10  parts  of  water,  is 
carefully  dropped  into  the  filtered  solution  obtained 
above,  and  the  legumin  is  precipitated;  an  excess  of 
the  acid  should  be  avoided,  as  this  would  dissolve  tbe 
precipitate.  It  falls  in  the  shape  of  white  flakes,  and 
after  having  been  washed  on  a  filter  should  be 
dried,  pulverized  and  freed  from  adhering  fat  by 
digestion  in  ether.  Legumin  may  be  obtained  from 
lentils  with  the  same  facility  as  from  peas;  but  it  is 


220  ORGANIC     CHEMISTRY. 

less  easily  procured  from  beans  (haricots),  in  con- 
sequence of  their  containing  a  gummy  matter  which 
interferes  with  its  precipitation  and  with  the  filtration 
of  the  liquids. 

The  cnemical  properties  of  legumin  are  identical 
with  those  of  casein. 

Liebig  supposes  that  grape-juice  and  other  vegetable 
juices  which  are  deficient  in  albumen,  derive  their 
fermentation  power  from  soluble  legumin.  This 
principle  is  soluble  in  tartaric  acid,  and  to  its  presence 
he  ascribes  the  tendency  of  sugar  to  toi-rn  alcohol  and 
carbon  dioxide  instead  of  mucilage  and  lactic  acid. 

VEGETABLE  ALBUMEN. 

Vegetable  albumen  is  contained  in  many  plant- 
juices  and  is  deposited  in  fiocculi  on  applying  heat  to 
such  liquids.  It  can' also  be  precipitated  by  nitric 
acid,  tannin  and  mercuric  chloride  brecisely  like  animal 
albumen.  Vegetable  albumen  is  composed  of  carbon, 
hydrogen,  nitrogen,  oxygen  and  sulphur.  There  is  no 
trustworthy  formula  for  this  substance. 


INDEX. 


PAGE. 

Acenapthene,  Ci2Hio=i54. .  38 
Acetamide,  C2  HS  NO=59- .  136 
Acetanilide,  Cs  K«  NO  — 135.  130 
Acetic  oxide  C4  H6  O3  =102  103 

Acetochlorhydric  glycol 63 

Acetone,  C3  H6  0=58 99,  108 

Acetyl  acetate,  C4  N9  Os  . . .  103 
Acetyl  chloride,  C2  C1H3  O.  103 
Acetyl  hydride  or  aldehyd, 

C2H40=44 86 

Acetylamine,  C2  HS  N=43..  129 

Acetylene,  C2  H2  =26 18 

Acetylide,  cuprous 19 

Acid,acetic,  C2  H4  Os  =60.  .  99 
Acid,  aconitic,  CG  HG  OG  =95  174 
Acid,  acrylic,  C3  H4  O2  =72.  91 
Acid,  adipic,  CG  HioO4  =148  91 
Acid,  alloxanic,  C4  H4  N2  Os  125 
Acid,  alpha-cymic,  QiHyOg  91 
Acid,  amalic,  CG  HT  N2  04  .  .  169 
Acid,  anchoic,  Cg  HieO4  =188  93 
Acid,  angelic,  C.5  HS  O2  =108  91 
Acid,  anisic,  Cs  I  Is  Os  =152.  92 
Acid,  arabic,  CG  HioOs —342  217 
Acid,  arichidic,  C-2oH4oO2  .  .  90 
Acid,  atropic.Cg  HS  O2  =148  164 
Acid,benzoic,C7  HG  O2  =126 

91,  109,  126 

Acid,  benzoglycolic 126 

Acid,  butyric,C4  H8  O2  .  .  90,  108 
Acid,  caffetannic 196 


Acid,  camphic, 
Acid,  carapholic,  CigHisC^  . .  91 
Acid,  camphoric,CioHisO4  41,  93 
Acid,  caprylic,  Cg  Hi6O2  ...  90 
Acid,  caproic,C6  Hi2O2  =  1 16  90 
Acid,  capric,  CioH2oO2  =172  90 
Acid,  carballylic,  CG  H8  OG  .  95 
Acid,  carbarn ic,  CHs  NO2  . . .  u 
Acid,  carbazotic,( Picric) 

CH3N3  07=229 33 

Acid,  carbolic, CG  H6  0  =  94.  32 
Acid,  carbonic, C2  H3  O  =  62.  92 

Acid,  catechic 196 

Acid,  cerotic,  CsTHsjO .  .  .90,  180 
Acid,  chelidonic,  CT  H4  OG  ..  95 
Acid,  chlorbenzoic,C?  HS  CIO 

=  130.5  ....    160 

Acid,  cholalic,  C24H4oO5  =408  95 
Acid,  cholesteric,  C8  HioO5  . .  95 
Acid,choloidic,C24H38O4  =  3oo  94 
Acid,  cinnamic,  Cg  II8  O2  = 

148 91,  in 

Acid,citraconic,  Cs  HG  04  93, 121 
Acid,  citric,  C6  Us  O7.Ha  O  = 

192+18 .- 120,  95 

Acid,  coccinic,  dsIIscOa  ...  90 
Acid,  comcnic,  CG  H4  Os  .. .  95 
Acid,  coumaric,  Cg  H8  O3  . .  93 
Acid,  croconic,  Cs  II2  Os  . .  95 
Acid,  crotonic,C4  HG  O2  ..91,  178 
Acid,  cumic,  CioHi2O2  =164  91 


222 


INDEX. 


PAGE. 

Acid,  cyanacetic, 

C2H3(CN)02=85 103 

Acid,cyanhydric,HCN  =  27.  161 

Acid,dextroracemic 117 

Acid,  dialuric,  C4  H4  N2  04  125 
Acid,  dinitrobenzoic, 

CT  H4(NO2)2  O2  =212...  no 
Acid,doeglic,  CigH36O2  =296  91 

Acid,  elaidic 177 

Acid,  erucic,  QzHgOg  =338.  91 
Acid,  ethalic,  CieHsaOg  =256  179 
Acid,  ethylsulphuric, 

C2H5HS04=i26 71 

Acid,  formic,  CH2  O2  =50.98,  90 
Acid,  fumaric,C4  H4  O4  =  1 16  93 
Acid,  gallic,  CT  H6  O5  .  .95,  197 
Acid,  glucic,  Ci2  H8  Og  =306  186 
Acid,  glyceric,  C3  H6  O4  . . .  93 
Acid,  gl y  colic,  C2  Hi  O3  .  60,  92 
Acid,  guaiacic,  Ce  Us  O3  . .  .  92 
Acid,  gummic,  Ci2  H^  On..  217 
Acid,  hippuric,  Cg  Hg  NO3  ..  125 
Acid,  insolinic,  Cg  HS  O4  . . .  94 
Acid,  itaconic,  Cs  He  O4  .  .  121 
Acid,  lactic,  C3  He  O.s  ..92,  122 
Acid,  lauric,  C^H^Oo,  =200  90 
Acid,  leucic,  Ce  Hi2O3  =132.  92 
Acid,  lichenstearic,  Cg  Hi4Os  92 
Acid,  lithic,  C5  H4  N4  O3  . .  123 
Acid,  lithofellic,  C2oH36O4  . .  93 
Acid,  malic,  C&  He  Os  =134  115 
Acid,  malonic,  Cs  H4  O4  ...  93 

Acid,  mannitic. . . . , 183 

Acid,  margaric,  CnHgiC^  . . .  177 
Acid,  meconic,  CY  H4  O. . . .  143 
Acid,  melissic,  CsoHeoOa  . .  90 


PAGE. 

Acid,  mellitic,  C4  H^  64  . . . .     94 
Acid,  mesoxalic,  Cg  H2  Os  . .    94 

Acid,  metagummic 217 

Acid,  monochloracetic, 

C2  Cl  HS  O2  =94.5 201 

Acid,  moringic,  CisH28O2  . .  91 

Acid,  morintannic 196 

Acid,  mucic,  CQ  HS  Os  =205  95 

Acid,  myristic,  C^HasO^o ...  90 

Acid,  cenanthalic,  CT  HuOg  90 

Acid,  cenanthic,  CuH-^Os  . .  92 

Acid,  oleic,  Ci8H34O2  =282.  91 

Acid,  opianic 127 

Acid,  oxalic,  C2  H2  O4  .  ..93,  1 12 

Acid,  oxamic,  C2  HS  NOs  . .  n 

Acid,  oxybenzoic,   Cy  HQ  Os  195 

Acid,  oxybutyric,  C4  HS  Os  92 

Acid,oxycuminic,  CioHi2Os  92 

Acid,oxynapthalic,  CioHe  O4  94 

Acid,  oxyvaleric,  Cs  HioOs  ..  92 
Acid,  palmitic,  CieHsoO^  .90,  177 

Acid,  parabanic,Cs  H2  No  Os  125 

Acid,  parafinic,  C24H4gO2  . .  23 

Acid,  paralactic 122 

Acid,paramalic,  C4  H4  O4  . .  116 

Acid,  paratartaric 117 

Acid,  pectic,  CieH22Os  =294.  218 

Acid,  pectosic 218 

Acid,  pelargonic,  Cg  HisO2  ...  90 

Acid, phenic,  Cg  H6  0=94.  .  32 
Acid,  phenylsulphuric, 

C6  H6  04  8=174 32 

Acid,  phloretic,  Cg  HioOs  . .  92 

Acid,  phtalic,Cs  H6  O4  =150  94 

Acid,  physetoric,  CieHsoO-^  . .  91 

Acid,  picric,  C6  H3  (NO2  )s  O  33 


INDEX. 


223 


PAGE. 

Acid,  pimelic,  CT  HnO±  93 

Acid,  pinariCjCaoHgoOa  =302  41 

Acid,  pinic,  CaoHsoOs  =  302 . .  91 

Acid,  piperic,  Ci2HioC>4  =218  94 
Acid,  propionic,  C3  HG  Oo  78,  90 

Acid,  prussic,  HCN=27.    . .  161 

Acid,  pyrogallic,  CG  H6  O3  . .  198 

Acid,  pyroligneous 100 

Acid,  pyromeconic,  C5  H4  O3  92 
Acid,  pyrotartaric,  Cs  H8  04 

=  i32 93,  "7 

Acid,  pyroterebic,  CG  HioOg  . .  91 
Acid,  pyru vie,  Cs  Ih  O3  —88  92 
Acid,quinic,  Ci  HioOc  =144-  93 

Acid,  quinotannic 196 

Acid,racemic,C4  H6  OG  =150  117 
Acid,  ricinoleic,  CisH^Os,  92,  180 
Acid,  roccellic,  Ci7Hs-)O4  .  .  93 
Acid,  salicylic,  CT  H5  O3  195,32,92 

Acid,  sarcolactic 122 

Acid,  scammonic,  CisH-^Os  92 
Acid,  sebic,  Ci0Hi8O4  =202..  93 
Acid,  sorbic,  Cc  I  Is  Og  =112.  91 
Acid,  stearic,  CisHsoOa  .  .90,  177 
Acid,  suberiCjCs  Hi4O4  =174  93 
Acid,  succinic,  C4  HG  0493,  115 
Acid,  sulphocarbolic, 

C6H6S04=i74 33 

Acid,  sulphoglucic 185 

Acid,  sylvic,  QoHsoOo  =302.  41 
Acid,  tannic,  C27lI>2Oi7=6iS  196 
Acid,  tartaric,C.i  HG  OG  .  ..116,  95 
Acid,  tartrelic,  C4  H4  O5  . . .  117 
Acid,  tartronic,  Qj  H4  Os  . .  94 
Acid,  terebic,C:  HioO4  =158  93 
Acid,  terechrysic,  CG  HG  O4  94 


PAGE. 

Acid,  thionuric, 

Ci  H5  NO3  SOs  =195 125 

Acid,  thymotic,  QiHuOs  ..  92 
Acid,  toluic,  Cs  HS  Og  =136  91 
Acid,  trichloracetic, 

HC2C13O2  =163.5 JO2 

Acid,  tropic,  Cg  HioOs  =166.  164 
Acid,  uric,Cs  H4  N4  Os  =  168  123 
Acid,  valeric  or  valerianic, 

CG  HioO2  =102 109,  90 

Acid,  veratric,  Cg  HioOs  ...  94 
Acid,  xylic,  Cg  HioO2  =150.  91 

Acids 95 

Acids,  aromatic 91 

Acids,  fatty 90 

Acids,  general  methods  of 

preparation, 96 

Acids,  organic 90 

Acids,  defined 95 

Acids,  polyatomic 112 

Acids,  pyro 97 

Aconitina,  C3oH47NO7  =533.  165 
Alcohol,  allyl,  C3H6O...45,  57 
Alcohol,  amylic,  Cs  11120.56,45 
Alcohol,  benzyl,  CT  H8  O=io8 

46 

Alcohol,  butyl,  C4  H]0O  =  64  45 
Alcohol,  eery  1,C27H56O  =  396  45 

Alcohol,   cholesteryl 46 

Alcohol,   cinnyl,  Cg  HioO . .     46 

Alcohol,  cuneol 46 

Alcohol,  cymol,  CioHuO..  46 
Alcohol,  melissic,  CsoHe2O. .  180 
Alcohol,  methyl,  CH4  O.  .45,  46 
Alcohol,  myricyl,  CsoHcsO..  45 
Alcohol, octyl,  Cs  Hi8O=i3o  45 


224: 


INDEX. 


PAGE. 

Alcohol,  ordinary,  or  ethyl, 

C2H60  =  46 49 

Alcohol,  propyl,  Cs  HS  O.. .  45 

Alcohol,  sexdecyl,  CieHaiO..  45 

Alcohol,  sextyl,  CQ  HuO 45 

Alcohol,  vinyl,  C2  H6  0  =  46  45 

Alcohol,  xylyl,Cs  HioO=  122  46 

Alcohols,  diatomic 58 

Alcohols,  monatomic 44 

Alcohols,  polyatomic. 59 

Alcohols,  sulphur 82 

Alcohols,  selenium 82 

Alcohols,  tellurium 82 

Alcohols,  tetratomic 59 

Alcohols,  triatomic 64 

Aldehyds 86 

Alizarin,   QoHe  Os  =174. . .  39 

Alkalamides 136 

Alkaloids 127 

Allantoin,    C4  H6  N4  O3  =  158 

I24 

Alloxan,  C4  H4  N2  Os  =160.  125 

Alloxantin,  Cg  HioN4  OIQ.  .  123 

Allyl  iodide,  C3  H5  I  =  168 . .  57 

Allyl  sulphide,  C6  HioS=  1 14  57 
Allyl  sulpho-cyanide, 

C4HsNS=99 57 

Allylamine,  Cs  Ht  N  =  57...  127 

Allylene,  Cs  H4  =40 20 

Amane,  Cs  Hi2=  72 23 

Amber 26,  42 

Amides 136 

Amidoxypropyl, 

C3H4(NH2)O=72 75 

Amines 133 

Ammelide 172 


PAGE. 
Ammonia  aldehydate, 

C2H4ONH3=6i 87 

Ammonia  citrate  of  iron. . .  121 

Ammoniacum 43 

Ammonias,  compounds 131 

Ammonium,  cyanate,CH4  N2  172 

Ammoniums 137 

Ammoniums,  quarternary. .  136 
Amygdalin,  CaoH^N On . . . .  193 
Amyl,  acetate,  CT  Hi4Os  . .  ,56 
Amyl,  chloride,  CsHnCl..  56 
Amyl,  hydride,  Cs  Hi2=72.  23 
Amylamine,  Cs  HisN  =  S7. .  121 

Amylene,  Cs  Hio=7o 23 

Anhydride,  tartaric, 

C4H4  05=132 117 

Aniline 30,127,  131 

Anthracene,  Ci4Hio=i78.  .29,  39 

Arabin  C^H^On  =  342 217 

Arbutin  dsH^C^  =284 193 

Aricina  CasH^Ng  O4  =397. .  129 

Arnicin  ....  42 

Aromatic  compounds 89 

Arsines 128 

Asphalt 26 

Assafoetida 43 

AtropiaCnHssNOs  =289.164,129 

Balsams 41 

Bases  organic, 125 

Bases  quarternary, 136 

Bassorin 218 

Belladona 164 

Benzene  Ce  He  =78 27 

Benzine 24 

Benzoic  aldehyd,  C7H6O..  86 
Benzol,  C6  H6  =  78 27 


INDEX. 


225 


PAGE. 

Benzene,  CO(Ce  H5  )2  =182  119 
Benzonitrile  CT  HS  N=iO9..  no 
Benzyl  chloride,  C7  H5  O  Cl  126 

Benzylene,  Ci5H28=2oS 20 

Bidecane,  Ci2H26=  170 28 

Bidecy  1  hydride,  Ci2H26=  1 70    23 

Bitumen 26 

Biuret,  C2  O2  H3  N3  =  1 13  •  •   i72 

Borneol,  CioHi8O  =154 58 

Brandy 52 

Brucia,  Caa  H26  N  O4, 4H2  O 

=  394+72 161,  129 

Butane  C4  Hio=s8 23 

Butter 179 

Butyl  hydride,  C4  H  10=58. .  23 
Butylamine,  C4  HnN  =  73-  ..  128 

Butylene,  C4  H8  =56 20,     22 

Cacodyl,  (CH  3)2  As 79,  105 

Caffeia  (caffeine), 

C8  Hi0N4  O=  194 130,  1 68 

Campholic  alcohol 117 

Camphor,artincial,CioHi6HCl  37 
Camphor,  CioHi6O  =  i52.. . .  40 
Camphor,  monochlor, 

CioH5iClO  =  186.5 41 

Camphor,  oxy-,  CioHi6O2  ...  41 
Camphor  of  Bornco,CioHi8O  58 
Cantharidin,  C5  H6  O2  =98.  168 

Candles, 176 

Cannabin...   42 

Caoutchouc,  (C5  H8  )x  ..., .  .36,  43 
Caprylamine,  C8  Hi9N=i29.  127 
Caramel,  CtaHisOg  ?=3o6. .  190 

Caramelaae, 190 

Caramelene,  190 

Carameline, 190 


PAGE. 

Carbo-hydrates,  defined, ....  7 
Carbonic  ether,  Cs  HioOs  . .  74 

Casein,  vegetable, 219 

Castor  oil, 180 

Castorin, 42 

Cellulose,  (cellulin,) 

(Ci8H3005) 202 

Cerasin 217 

Cetene,  CnH22=  154 23 

Chitin 184 

Chloral,  C2  C13  HO=  147.5 . .  87 
Chloral  hydrate, 

C2  HCl+2HO=6o.5+63...  88 
Chloroform,  CHCls  =119.5.  47 
Chloropropyl,C3  H6  €1  =  77.5  15 
Cholesterophan,  Cs  He  N2  Os  169 
Cinchonia,  (cinchonine) 

C20H24N2  0  =  308 129,  156 

Cinchonicia,  (cinchonicine) 

CaoH24N2  02  =308 158 

Cinchonidia,  (cinchonidine) 

C20H24N2  0  =  308 158,  129 

Cinnamene,  C8  H8  =104..  . .  38 
Codeia,  CisH-^NOs  =299.146,129 

Colchinia 163 

Collodion 208 

Colophony 41 

Compound  ammonias 131 

Conia,  (conine),  C8  Hi5N.i4i,  129 
Conicine,  C8  iri5N=i25  . . . .  129 
Coniferin,  Ci6H22Os  =342  . .  193 

Convolvulin,  CsiHsoOie 193 

Conylia,  C8  Hi5N=i25.  .141,  129 

Cotarnine 147 

Cream  of  Tartar,  C4  H5  KOe  116 
Creatin,  C4  H9  N3  O->  =  131 .  188 


226 


Creosote 34 

Cresylol,  C7  H8  O=io8  . ..  29,  34 
Crotonylene,  C4  HG  =54. . . .  20 

Cumene,  Cg  IIio=i2o. 28 

Cumidine,  C9  IIi3N=i35 127 

Cuprous  acctvlide, 

Cu4  C4  II2  0=319.6 20 

Cui-ari 163 

Curarina 162 

Cyanopropyl,  C3  H6  (CN). . .  15 
Cyclamin,  C^U24OiQ=  424 . .  193 

Cymene,  Ci0Hi4=  134 2^  3s 

Cymogene, 24 

Cymol,  CioHi4=i34 41 

Daphnin,  CaiHaiOn 193 

Daturia,  (atropia) 

CnH^NOs  =289 164,  129 

Decane,  CioH-22— 142 24 

Dextrin,  CG  HioOs  =162.212,214 

Diastase 212 

Diethylamine,  C4  HnN=y3.  128 
Diethylpropyl, 

C3H5(C2H5)2=99 15 

Diethylenic  diamine, 

C4  Hi0N2=86 170 

Digitalin 166 

Digitin 166 

Dimethylphosphine,C2  H7  P  128 

Draconyl 38 

Dulcite,  (dulcose) 

C6  IIi-iO6  =126 183,  181 

Duodccylene,  Ci2ll24=  168. .  23 

Elaidine 175 

Elaine 175 

Elayl,  C2  H4  =28 21 

Elemi 43 


PAGE. 

Emetia,  CisH-^NOs  =248. . .  167 

Emetics 119 

Ergotin 42 

Ery thrite,  C4  Hi0O4 49 

Esculin,  QjiHojOis 193 

Essence  of  mirbane, 

C6H5N02=i23 29 

Essence  of  thy  me,CioHi6 34 

Essential  oil  of  cloves,C1()Hi6  37 

Essl.  oil  of  bergamot 37 

Essl.  oil  of  copaiba,  CsoHss. .  37 

Essl.  oil  of  cubebs,  CjjoHgg.. .  37 

Essl.  oilofelemi,  CioHi6=i36  37 

Essl.  oil  of  juniper,  QoHig. .  .  37 

Essl.  oil  of  lemon,  Collie 37 

Essl.  oil  of  orange,  CioII16.  ..  37 

Essl.  oil  of  pepper,  CioHie ...  37 

Ethal,  CieHwQz  =258 179 

Ethane,  C2  H6  =30. . .  .13,  15,  23 

Ethene,  Co  H5  =29 13,  15 

Ether  acetic, 

C2  H5  C2  H8  Oa  =88 73 

Ether,  butyric,  C6  Hi2C>2  =11681 

Ether,  chlorhydric,  C2  H5  Cl.  75 

Ether,  common,  C4  HioO  =  74  70 

Ether,  cyanhydric,  Cs  H5  N .  77 

Ether,  ethyl,  C4  HIQ=  74 70 

Ether,  formic,  C%  HQ  O2  ==74.  Si 

Ether,  hydroiodic,  C2  H5  I. .  76 
Ether,  hydrosulphuric, 

C4Hio*S=90 83 

Ether,  cenanthylic, 81 

Ether,  oxalic,  CG  IIioO4  =  146  74 

Ether,  oxamic,  C4  H7  O3  N.  117 

Ether,  sulphuric,  C4  HioO. .  70 

Ether,  valerianic, 81 


INDEX. 


227 


PAGE. 

Ether,  vinic,  C4  HioO  =  74. . .  70 

Ethers 69 

Ethers,  simple 69 

Ethers,  compound 73 

Ethers,  miscellaneous Si 

Ethers,  mixed 38 

Ethine,  C2  H2  =26 13 

Ethyl,  C2  Hs  =29 15 

Ethyl  chloride,  C2  H5  Cl .. .  75 

Ethyl  cyanide,  C2  H5  CN..  .  77 

Ethyl  formiate,  C2  HG  O2  . . .  9 

Ethylglycol,  C4  H9  O2  =89.  61 

Ethyl-hcxyl  ether,  C8  HisO..  84 

Ethyl  hydride  Co  1 15  =  30  . . .  23 

Ethyl  iodide,  C2  H5  1  =  156..  76 

Ethyl  mercaptan,  €4  H6  S,..  83 

Ethylmethylaniline,  Cg  HisN  30 

Et-hyl  oxide  C4  HioO  =  14... .  69 

Efchyl  sulphide  C4  HioS  =  90..  83 

Ethylamine,  C2  H7  N.  . .  132,  127 

Ethylene,  C2H4  =28 21 

Ethylene  bromide,  C2  H4  B2  61 

Ethylene  chloride,C2  H4  C12  76 

Ethylene  oxide,  C2  H4  O..  . .  62 

Eucalin,  C6  HioOe  — 180 182 

Fats 174 

Fatty  acid  series 90 

Fermentation,  acetic 100 

Fermentation,  alcoholic.  .49,  181 

Fermentation,  gallic 197 

Fermentation,  lactic 122 

Ferrocyanide  of  potassium, 

K4FeC6N6=36S 172 

Flour 215 

Formene,  CH4  =16 23 

Frankincense 43 


PAGE. 

Fulminates 54 

Fusel,  or  fousel  oil 56 

Galactose,  C6  Hi2O6 187,  182 

Gas,  illuminating 21 

Gasolene 24 

Glucosane,  CG  H^Oe  =  180  .   185 
Glucose,  C6  IIiijOc  =  iSo.  182, 184 

Glucosides 192,  184 

Gluten 216 

Glycerin,  Ca  HS  Os  =92. ...     64 
Glycocol,  Zincic, 

Zn(C2H4  NO2)2  =213.2.  126 
Glycogcn,  CG  HioOs  =162. .  214 
Glycol,  amyl,  €5  Hi2O2  =  104  59 
Glycol,  butyl,C4  HioOg  =90.  59 
Glycol,  diethyl,  C6  Hi4O2  .  .  61 
Glycol,  ethyl,  C4  1 19  O2  =89  61 
Glycol,  hexyl,C6  H4  O2  =  1 18  59 
Glycol,  monochlorhydric.  ..  62 
Glycol,  octyl,C8  Hi3O2  =  146  59 
Glycol, ordinary,  C2  HG  Og  ... .  59 
Glycol,  propyl,  C  3II8  O^  .58,  123 

Grape  sugar 182 

Guano 124 

Gum,  CG  HjoOs  =  162 216 

Gum  arabic 217 

Gum  resins 41 

Gun-cotton 207 

Helicin,  dsH^O?  =283 194 

Heptyl  hydride,  CT  HI<J=  100.     23 

Heptane,  C7lli6=ioo 23,24 

Heptylene,   C?  Hi4=98 22 

Hexadecane,  Ci6Hsi=227. ...    24 
Hexadecyl  hydride,  CioIIs^.     24 

Hexane,  C6  Hi4=S6 23 

Hexylene,  C6  Hi2=84 22 


228 


INDEX. 


PAGE. 

Hexyl  hydride,  C6  Hu=86..     23 

Hoffmann's  anodyne 73 

Homologous   series 12 

Honey 192 

Hydrides 23 

Hydrocarbons 18 

Hydrocarbides 18 

Hydrocarbides,   extra-terres- 
trial       40 

Hydrogen  carbides 18 

Hydrosulphuric  ether, C  4HioS  83 
7:lyosciamine,CnH23NO3  129, 164 

j  ndigo 130 

Inosite,  (inosin)Ce  H^Oe  187, 182 

Inuline,  CG  HioOs  =162 214 

lodomorphia 145 

Isatin,  C8  H5  NO2  =147 38 

Isologous  series 12 

Isomerism 8 

Jalappine,  C34H56Oic>=7i6...  193 
Jerria,  C2oH46N2  O3  =362.. .  163 

Kerosene 24 

Kctones 40 

Lactide,  C$  H4  O2  =72 123 

Lactose  or  lactin, 

CiaHaiOi2=342 . .  .191,  182 

Leather 197 

Legumin 219 

Levulosan,  CG  HioO.5  =  162..  190 
Levulose,C6  Hi2O6  =180.187,182 

Lichenin 214 

Madder 39 

Maltose,  C6  HiaO6  =  180 182 

Mannitane,  CG  H^Os  =164..  183 
Mannite,  C6  Hi4O6  =182.181,183 
Marsh-gas,  CH4  =  16 23 


PAGE. 

Meconine, 143, 147 

Melampyrite,  CG  H^O  6=184  181 
Melezitose,  Ci2H22Oi3=374-.  182 

Melitose,  Ci2H^Oi2=365 182 

Mercaptans 82 

Metamerism 9 

Metaterebenthene,  CsoHss. .  38 

Metastyrol, 38 

Methane,  CH4  =  16 13,  15,  23 

Methenyl,  CH=i3 15 

Methyl,  CH3  =15 15 

Methyl  acetate,  63  H6  Og  ...  9 
Methyl  chloride,  CH3  Cl.. . .  47 
Methyl  cyanate,  Ca  HS  NO..  131 
Methyl  hydride,  CILi  =16..  23 
Methylamine,  CH5  N. .  .  127,  131 
Methylethylamine,  C3  H9  N  128 
Methylphosphme,  CH5  P. . .  128 
Methylpropyl,  C3  H6  (CH3  ).  15 

Molasses 189 

Monamines 133 

Monochlorcamphor, 

CioH15C10  =  S6.5 41 

Monochlorhydrin, 

C3H7C102=  110.5 66 

Morphia,  (Morphine) 

Ci-H19N  03=285 143,129 

Murexide,C8  HS  N6  OG  =284  125 
My  cose,  Ci^H^OiisJ^. . . .  182 

Naphtha 24 

Naphthalamine,  CioHg  N. . .  128 
Naphthalin,  CioH8  =128..  .27,  38 
NarceiajC^HogNOg  =463.148,129 
Narcotina,  C22H23NOr  =413  129 
Nicotina,  CioHi4N2  =  162 . 139,129 
Nicotyl,  C5  H7  =67 140 


INDEX. 


229 


PAGE. 

Nicotylia,CioHi4N2  =162.139,129 

Nitrile  bases 124 

Nitrobenzol,  C6  H5  NO2  ....  29 
Nitroglycerine, 

C3  H5  (NO2  )3  O3  =227 ...  66 

Nitryls  or  cyanhydric  ethers,  134 

Nonane,  Cg  HSO=  128 23 

Nonyl  hydride,  Cg  H20=  128.  23 

Nonylene,  Cg  His=i26 22 

Octane,  Cs  His=ii4 23 

Octyl  glycol,  Cs  Hi8O2  =146  59 

Octyl  hydride,  Cs  H\8=  1 14. .  23 

Octylene,  Cs  Hie=ii2 22 

Oils,  fatty 174 

Oils,  essential 36 

Olein,  C57Hio4  OG  =884 175 

"Oleomargarine" 179 

Oleo-resins 42 

Opium 142 

Orcin,  C?  HS  O2  =124 193 

Organizable  substances 205 

Organometallic  compounds,  78 

Oxamide,  C2  H4  O>  No  =92,  74 

Oxanthracene,  Cyllg  O2  ...  .  39 
Oxycamphor,  CioIIitjOo,  =168  41 

Para-arabin 192 

Plants,  respiration  of. 201 

Plants,  nutrition  of 204 

Polyamines  . .  170 

Polymerides 9 

Polymerism, 9 

Populin,  QaoH^Os  =390. . . .  193 

Potassium,  binoxalatc 114 

Potassium,  ferrocyanide, 

KiFeCeN6=368 172 

Paraffin,  Co4H5  0  =  338  ...  .22  24 


PAGE. 

Papaverine,  C2oH2iNO4  .129,  148 
Paramorphia,  CigHaiNOs  ...  148 
Paramylene,  CioH2o=  140. . .  22 

Pectin 218 

Pectose 218 

Pentadecane  0^32=212. . .  24 
Pentadecyl  hydride,  CisH^.  24 

Petroleum 24 

Phenol,  C6  H  6O  =  94 32 

Phenol,  potassic  C6  H5  KO..  32 
Phenol,  trinitric 

C6H3(NO2)3  0  =  229 30 

Phenyl,  CG  H5  =77 30 

Pheny  1  hydrate,C  CH6  O  =  94  32 
Phenylamine,  CG  H  7^=93.  127 
Phlorizin,  C2iH24Oio=436. . .  193 

Phlorylol,  C8  Hi0O=i22 34 

Phosphines 128 

Phtalidamine,  Cs  Hg  N=ii9  127 
Picrotoxin,  C3  H6  O2  =98...  169 

Pinite,  C6  H12O5  =  164 in 

Piperidine,  C.5  HnN=85..i3o,  141 
Piperine,  CnHigNO3  =285..  .141 

Pitch,  Burgundy 42 

Potassium,  formiate 88 

Propane,  C3  H8  =44  ...  13,  15,  23 

Propenyl,  C3  HS  =41   15 

Propine,  C3  H4  =40 13 

Propone,  C3  H2  =38 13 

Propyl 15 

Propyl  hydride,  C3  HS  =44-  23 
Propylamine, C3  Hg  N  =  59. .  127 

Propylene,  C3  HG  =42 22 

Proplene  iodide,C3  HS  I  =  i68    64 

Ptyalin 212 

Pyrethrin 42 


230 


INDEX. 


Pyrolignite 106 

Pyroxylin 207 

Quercite,  C6  Hi2O3  =  164.  . .  181 
Quercitrin,  C^U.g[)Cn=6^o. .  193 
Quinia,  (quinine) 

C2oH24N2  O2  =324 151,  129 

Quinicia,  C2oH24N2  O2  . .  154,  129 
Quinidia,  C2oH24N2  O2  =324.  129 

Quinidia,  oxalate  of 155 

Quinoidine 158 

Quinoleine,  (Quinoline),  ' 

130,  I53>i57 

Quinovin,  CsoH48C8  =  536. . .  193 

Radicles,  defined 14 

Radicles,  organometallic 78 

Radicles,  organometalloid. ..  Si 

Reagent,  Fehling's 187 

Reagent,  Haines' 187 

Reagent,  Trommer's 186 

Resins 25,  41 

Retinasphalt 25 

Retinite 25 

Rhigolene 24 

Rice 216 

Rochelle  salt, 

KNaC4  H4  O6 +4  aq  ....  118 
Rosaniline,  CsoH^Ns  0  =  319  31 

Rutylene,  CioHi8=  138 20 

Rye 216 

Saccharide 186 

Saccharoses,  Ci2H22On  = .  1 89, 1 82 

Salicin,  Ci3Hi8O7  =286 194 

Saligenin,  C7  H8  O2  =124.. .  194 

Saponification 176 

Saponine 193 

Sinapoline,  C7  Hi2N2  0=140  58 


PAGE. 

Sinnamine,  C4  H6  N2  =82.  .  58 

Soaps 1 76 

Sodium  ethyl,  C2  H5  Na=52  So 
Sodium  sulphocarbolate, 

NaC6H6S04=i97 33 

Solanidia,  (solanidine) 165 

Solania,  (solanine) 

C43H7iNOi6=857..  .165,129,193 

Sorbin,  Ce  Hi2O6  =  180 182 

Spermaceti,  C32H64O2  =480  179 

Spirit  of  Mindererus 105 

Stannethyl 79 

Stannethyl  iodide 79 

Starch 210 

Stearin,  (stearine) 

Cs-Hno  06=890 174 

Stearine  candles 176 

Stibines 128 

Stibyl 119 

Strychia,  (strychnine), 

C2iH22N2  62  =334.  . .  159,  129 

Styrol,  C8  H8  =  104 38 

Sucrates 190 

Sugars 181 

Sugar  of  milk,  Ci2H;>4Oi2. 191,182 

Tannin,  C27H22Oi7=6iS..  196,  193 
Tartar  emetic, 

KSbC4H4O7  =325 118 

Tetrachloropropyl, 

C3H3Ci4=i8i 15 

Tetradecane,  Ci4Hso=  198.  .  .  24 

Tetradecyl  hydride,  Ci4II3o. .  24 

Tetradecylene,  Ci4H28=i96.  22 
Tetrethylammonium, 

N(C2H5)4=i3o 133 

Thebeia,Ci9H2iNO  3 148,  120 


INDEX. 


231 


PAGE. 

Theia,  (theine) 

C8  Hi0N4  O2  =  194-  •  •  - 168>  J30 
Theobromine, 

C7  HS  N4  O2  =  180. . . .  169,  130 

Thymol,  CioHi4O=  150 34 

Thiosinnamine, 

C4H8N2S=ii6 58 

Tobacco 140 

Toluene,  C?  H8  =92 28 

Toluidine,C7  H9  N=  107..  127, 130 
Trehalose,  Ci2HooOn  =  342. .  182 
Trichlorhydrin,  Cs  H5  Cls  . .  66 
Trichloroxypropyl, 

C3  H2  C13  O=  160.5 15 

Tridecane,  CisHss— 184 27 

Triedecyl  hydride,  CisHsg. .  24 
Tridecylene,  Q3Ho6=  182  ...  22 
Triethylamine,C6  HiSN=  101 . 135 
Triethylarsine,  C6  Hi5As  ....  128 


PAGE. 

Triethylenic,  diamine, 

CG  Hi2O-2  =112 170 

Triethylstibine,  C6  Hi5Sb  ...  128 
Trimethylamine,  Cs  Hg  N...  128 
Trimethylphosphine,C3  Hg  P  128 
Tunicine,  (Ce  HioOs  )x,. .  184,  209 

Turpentine,  CioHi6=  136 35 

Types,  organic 10 

Wax 179 

Whiskey 52 

Wines 32 

Wood-spirit 49 

Xylene,  C8  Hio=io6 28 

Xylidine,  C8  HnN=i2i 127 

Xylyl  alcohol,  C8  Hi0O=  122.  46 
Zinc,  ethyl, 

(C2H5)2Zn  =  213.2. 79 

Zinc,  glycol, 

H4  NO2  }z  =21^.2...^,  126 


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